Gas barrier film, gas barrier film manufacturing method, resin substrate for organic electroluminescent device using the aforesaid gas barrier film, and organic electroluminescent device using the aforementioned gas barrier film

ABSTRACT

A gas barrier film comprising a resin substrate provided thereon at least one layer of a ceramic film, wherein the density ratio Y (=ρf/ρb) satisfies 1≧Y≧0.95 and the ceramic film has a residual stress being a compression stress of 0.01 MPa or more and 100 Mpa or less, wherein ρf is the density of the ceramic film and ρb is the density of a comparative ceramic film being formed by thermal oxidation or thermal nitridation of a metal as a mother material of the ceramic film so as to being the same composition ratio of the ceramic film.

FIELD OF THE INVENTION

The present invention relates to a gas barrier film mainly used asmaterials for packaging foods and pharmaceuticals, package forelectronic devices, or as display materials of a plastic substance fororganic electroluminescent device and liquid crystal; a method ofmanufacturing this gas barrier film; a resin substrate for organicelectroluminescent device using this gas barrier film; and an organicelectroluminescent device.

BACKGROUND

In the conventional art, a gas barrier film having a thin film ofmetallic oxide such as aluminum oxide, magnesium oxide and silicon oxideformed on the surface of a plastic substrate and film has beenextensively used to package the products that require interception ofvarious types of gases such as vapor and oxygen, as well as to packagethe foods and industrial products to prevent them from beingdeteriorated. In addition to packaging purposes, the gas barrier filmhas also been used as a substrate for a liquid crystal device, solarbattery and organic electroluminescent device (hereinafter referred toas “organic EL”) or the like.

An aluminum foil is widely used as a packaging material in this field.However, the problem with this material is that effective method forwaste disposal has not yet been found out after use, and the contentspackaged in the aluminum foil cannot be identified from outside becauseit is basically non-transparent. Further, transparency is very importantwhen used as a display material, and an aluminum foil completely failsto meet this requirement.

The substrate made of a polyvinylidene chloride resin or a copolymerresin made of vinylidene chloride and other polymer, or a material withgas barrier function provided by coating these vinylidene chloride-basedresins on a polypropylene resin, polyester resin and polyamide resin isextensively used as a packaging material in particular. However, sincechloride-related gases are produced in the process of incineration, thismaterial is seen as creating an environmental problem. Further, its gasbarrier function is not always satisfactory, and this material cannot beused in the field wherein a high degree of barrier function isessential.

The transparent substrate that is applied to the liquid crystal deviceand organic EL device to a greater extent. In addition to therequirements for less weight and greater size, sophisticatedrequirements such as long-term reliability, freedom in the shape anddisplay on a curvature are being imposed on such a substrate. Thus, sucha film substrate as a transparent plastic is coming into use, instead ofa glass substrate that is vulnerable to cracks and is difficult toincrease the space. For example, the Unexamined Japanese PatentApplication Publication No. H2-251429 and Unexamined Japanese PatentApplication Publication No. H6-124785 disclose an example of using ahigh molecular film as a substrate of the organic electroluminescentdevice.

However, the substrate such as a transparent plastic has a bas barrierfunction inferior to that of glass. For example, when a substrate ofinferior gas barrier function is used as a substrate of the organicelectroluminescent device, the organic film will be deteriorated bypermeation of vapor and air, with the result that light emittingfunction or durability will be lost. Further, when a high molecularresin substrate is used as an electronic device substrate, oxygen willpass through the high molecular resin substrate to enter the electronicdevice, wherein oxygen will spread and deteriorate the device. Further,the degree of vacuum required inside the electronic device cannot bemaintained.

Such problems have been left unsolved.

One of the known techniques to solve the aforementioned problemsprovides a method of producing a gas barrier film substrate by forming athin film of metallic oxide on a resin film. Known gas barrier filmsused as a packaging material or liquid crystal display device areexemplified by the gas barrier film formed by vapor deposition ofsilicon oxide on a plastic film (e.g., Patent Document 1) and the filmformed by vapor deposition of aluminum oxide thereon (e.g., PatentDocument 2).

One of the methods for meeting the requirements for a high degree ofvapor cutoff property proposed so far is the technique of producing agas barrier film formed by alternate lamination of a compact ceramiclayer and a flexible polymer layer for reducing the external impact(Patent Documents 3 and 4).

However, despite the description of the Patent Documents 3 and 4, thereare problems with the adhesion between the substrate and ceramic film(layer), and stability against chronological change in particular. Thebarrier function is comparatively satisfactory in the initial phase buttends to be reduced in repeated thermal tests. Thus, there has been aintense demand for a gas barrier film characterized by superbflexibility and excellent barrier function.

Patent Document 1: Unexamined Japanese Patent Application PublicationNo. S53-12953 (Tokkosho)

Patent Document 2: Unexamined Japanese Patent Application PublicationNo. S58-217344 (Tokkaisho)

Patent Document 3: U.S. Pat. No. 6,268,695 (Specification)

Patent Document 4: U.S. Pat. No. 6,413,645 (Specification)

DISCLOSURE OF INVENTION Problems to be Solved by the Invention

The object of the present invention is to provide a highly durable gasbarrier film containing a compact ceramic film characterized by superadhesion with a resin film substrate and high resistance to cracks; amethod of producing this gas barrier film; a resin substrate for organicelectroluminescent device using this gas barrier film; and an organicelectroluminescent device.

Means for Solving the Problems

According to the studies made by the present inventors, the problem withthe stability of the gas barrier film characterized by the improvedproperty of cutting off vapor and gas is found in inferior adhesionbetween the resin film and ceramic layer, and initial barrier functionis deteriorated in a durability test such as repeated thermo testsbecause compressive stress is generated inside the film when the filmdensity is increased for the purpose of enhancing the gas barrierfunction. Accordingly, even if this stress is reduced by a polymer filmor the like, deterioration in repeated thermo test or the like cannot bereduced very much. Improvement of the barrier function can be achievedby adjusting the stress of the film as the essential component so that avery slight compression stress occurs, and by increasing the filmdensity. This principle has been found out by the present inventors. Theaforementioned object of the present invention can be achieved by thefollowing structure.

1. In a gas barrier film having at least one layer of a ceramic film ona resin substrate, the gas barrier film characterized in that when thedensity of the ceramic film is ρf and the density of a comparativeceramic film formed by thermal oxidation or thermal nitridation of ametal being a mother material of the ceramic film so as to has the samecomposition ratio of the ceramic film is ρb, a density ratio Y of(ρf/ρb) satisfies a formula of (1≧Y≧0.95) and the ceramic film has aresidual stress being a compression stress of 0.01 MPa or more and 100Mpa or less.2. The gas barrier film described in the above 1, characterized in thatthe residual stress is 0.01 MPa or more and 10 Mpa or less.3. The gas barrier film described in the above 1 or 2, characterized inthat a material constituting the ceramic film is a silicon oxide, asilicon oxide-nitride, a silicon nitride, of an aluminum oxide, or amixture thereof.4. A resin substrate for an organic electroluminescent elementcharacterized in that a transparent conductive thin film is formed onthe gas barrier film described in any one of the above 1 to 3.5. An organic electroluminescent element characterized in that theorganic electroluminescent element is formed by coating aphosphorescence emitting organic electroluminescent material and a metallayer being a cathode on the resin substrate described in claim 4 for anorganic electroluminescent element and further by sealing with adhesionof a metal foil laminated on a resin layer.6. The organic electroluminescent element described in the above 5,characterized in that the metal foil laminated on the resin layer islaminated on the resin at a side of the metal foil where the metal foildoes not come in contact with the metal layer becoming the cathode andthe metal foil has a ceramic layer at a side of the metal foil where themetal foil comes in contact with the metal layer becoming the cathode,wherein the density of the ceramic film is ρf, and when the density of acomparative ceramic film formed by thermal oxidation or thermalnitridation of a metal being a mother material of the ceramic film so asto has the same composition ratio of the ceramic film is ρb, a densityratio Y of (ρf/ρb) satisfies the formula of (1≧Y≧0.95) and the ceramicfilm has a residual stress being a compression stress of 0.01 MPa ormore and 100 Mpa or less.7. In a method of manufacturing a gas barrier film by exciting a gascontaining a thin film forming gas with a high frequency electric fieldunder atmospheric pressure or a pressure close to the atmosphericpressure and exposing a resin substrate to the excited gas so as to format least one layer of a ceramic film on the resin substrate, the methodcharacterized in that when the density of the ceramic film is ρf and thedensity of a comparative ceramic film formed by thermal oxidation orthermal nitridation of a metal being a mother material of the ceramicfilm so as to has the same composition ratio of the ceramic film is ρb,a density ratio Y of (ρf/ρb) satisfies the formula of (1≧Y≧0.95) and theceramic film has a residual stress being a compression stress of 0.01MPa or more and 100 Mpa or less.

Effects of the Invention

The present invention provides a highly durable gas barrier filmcontaining a compact ceramic film characterized by superb adhesion witha resin film substrate and high resistance to cracks, and a method ofproducing this highly durable gas barrier film, as well as a resinsubstrate for organic electroluminescent device, and an organicelectroluminescent device by using this gas barrier film.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the relationship between the residual stressand degree of vacuum of the silicon oxide film formed by vacuum vapordeposition method;

FIG. 2 is a schematic diagram showing the layer structure of the gasbarrier film of the present invention;

FIG. 3 is a schematic view showing an example of the jet typeatmospheric pressure plasma discharge processing apparatus preferablyused in the present invention;

FIG. 4 is a schematic view showing an example of the atmosphericpressure plasma discharge processing apparatus for processing asubstrate between the opposing electrodes, preferably used in thepresent invention;

FIG. 5 is a perspective view showing an example of the conductivemetallic base material of the roll rotating electrode shown in FIG. 3and the structure of the dielectric covering the metallic base material;

FIG. 6 is a perspective view showing an example of the conductivemetallic base material of rectangular electrode shown in FIG. 3 and thestructure of the dielectric covering the metallic base material;

FIG. 7 is a schematic view showing the cross section of an organicelectroluminescent device sealed with the gas barrier film of thepresent invention;

FIG. 8 is a schematic view showing an example of the display apparatusmade up of an organic electroluminescent device;

FIG. 9 is a schematic view showing the display section A.

FIG. 10 is a schematic view showing a pixel; and

FIG. 11 is a schematic view showing a display apparatus of passivematrix structure.

DESCRIPTION OF REFERENCE NUMERALS

-   -   1, 2 Gas barrier film    -   3 Ceramic film    -   3′ Polymer-containing layer    -   Y Resin film substrate    -   10, 30 Plasma discharge processing apparatus    -   11 First electrode    -   12 Second electrode    -   14 Processing site    -   21, 41 First power source    -   22, 42 Second power source    -   32 Discharge space (between opposing electrodes)    -   35 Roll rotating electrode (first electrode)    -   35 a Roll electrode    -   35A Metallic base material    -   35B, 36B Dielectric    -   36 Rectangular fixed electrode group (second electrode)    -   36 a Rectangular electrode    -   36A Metallic base material    -   40 Electric field application means    -   50 Gas supply means    -   52 Gas inlet    -   53 Exhaust outlet    -   F Substrate    -   G Gas    -   G^(o) Gas in plasma form

BEST MODE FOR CARRYING OUT THE INVENTION

The following describes the best form of embodiment without the presentinvention being restricted thereto.

The gas barrier film of the present invention is an laminated filmhaving at least one layer of ceramic film formed on a resin film. It isa resin film having a ceramic film formed in such a way that thespecific density Y (=ρf/ρb) will be 1≧Y>0.95, wherein the density ofthis ceramic film is ρf, and the density of the ceramic film formed bythermal oxidation or thermal nitriding of the ceramic base materialconstituting the ceramic film having the same percentage composition asthat of this ceramic film is ρb. This ceramic film preferably has aresidual (internal) stress of 0.01 MPa or more without exceeding 100MPa. This arrangement provides a highly durable gas barrier film ofexcellent gas barrier function, having a vapor permeability of 0.1g/m²/day or less, preferably 0.01 g/m²/day or less, and an oxygenpermeability of 0.1 ml/m²/day or less, preferably 0.01 ml/m²/day, asmeasured according to JIS K7129B.

The following describes the components constituting the gas barrierfilm:

The gas barrier film (layer) of the present invention will be described.There is no restriction on the composition of the gas barrier film ofthe present invention if it is a film that blocks passage of oxygen andvapor. The material constituting the gas barrier film of the presentinvention is preferably an inorganic oxide as exemplified by the ceramicfilm of silicon oxide, aluminum oxide, silicon oxynitride (siliconoxide-nitride), aluminum oxynitride (aluminum oxide-nitride), magnesiumoxide, zinc oxide, indium oxide and tin oxide.

The optimum thickness of the gas barrier film of the present inventiondiffers according to the type and structure of the material to be used,and is selected accordingly. The preferred thickness is 5 through 2000nm. If this thickness of the gas barrier film is below this range, auniform film cannot be obtained, and satisfactory gas barrier functioncannot be ensured. The thickness of the gas barrier film is above thisrange, flexibility cannot be easily accorded to the gas barrier film.The gas barrier film may be subjected to cracks due to external factorssuch as bending force or tension after film formation.

In the present invention, the ceramic film as a gas barrier film formedon the resin film should be formed in such a way that the specificdensity Y (=ρf/ρb) is 1≧Y>0.95, when the ceramic film formed by thermaloxidation or thermal nitriding of the base material has a density of ρb,so as to get the same percentage composition as that of this ceramicfilm, assuming that the density thereof is ρf. The specific density Y(=ρf/ρb) is preferably 1≧Y>0.98.

In the present invention, the density of the ceramic film formed on theresin film can be obtained by the commonly known technique of analysis.In the present invention, the value obtained by X-ray reflectivitymethod will be used.

For the outline of the X-ray reflectivity method, reference should bemade to “X-ray Diffraction Handbook”, P. 151 (edited by Rigaku DenkiCo., Ltd., 2000, International Document Publishing Co., Ltd.) and“Chemical Industries”, No. 22 January. 1999.

The following describes a specific example preferably used in thepresent invention:

This is a method of measurement by applying X-rays to a substance havinga flat surface at a very small angle, using a measuring instrument ModelMXP21 manufactured by MacScience Inc. Copper is employed as a target ofthe X-ray source, and operation is performed at a voltage of 42 kV withan amperage of 500 mA. A multi-layer film parabolic mirror is used as anincident monochrometer. A 0.05 mm×5 mm incident slit and a 0.03 mm×20 mmlight receiving slit are employed. According to the 2θ/θ scanningtechnique, measurement is conducted at a step width of 0.005° in therange from 0 to 5°, 10 seconds for each step by the FT method. Curvefitting is applied to the reflectivity curve having been obtained, usingthe Reflectivity Analysis Program Ver. 1 of MacScience Inc. Eachparameter is obtained so that the residual sum of squares between theactually measured value and fitting curve will be minimized. From eachparameter, the thickness and density of the lamination layer can beobtained. The film thickness of the lamination film of the presentinvention can also be evaluated according to the aforementionedmeasurement of reflectivity.

This method can be used, for example, to measure the density (ρf) of theceramic film made of silicon oxide, silicon nitride and siliconoxynitride formed by the atmospheric pressure plasma method (to bedescribed later) or atmospheric pressure vapor deposition method.

The aforementioned ceramic film is required to be compact and ispreferably kept within the aforementioned range in terms of the specificdensity Y (=ρf/ρb) which is the ratio of the bulk to be the compositionwith respect to the density (ρb) of the ceramic (silicon oxide of thebulk when the ceramic film to be formed is a silicon oxide film). Thispreferably provides the degree of compactness which is close to that ofthe bulk. The method to produce the aforementioned film stably ispreferable.

The density of the ceramic film formed by thermal oxidation or thermalnitriding of the base material of the ceramic film formed by vapordeposition or plasma CVD so as to have the same percentage compositionas that of the ceramic film as a gas barrier film formed on the resinfilm is used for the aforementioned bulk film. The base material,namely, the silicon substrate is used as the base material in the caseof the silicon oxide.

Formation of the silicon oxide film by thermal oxidation of siliconsubstrate is widely known. A thermally oxidized film is formed on thesurface of the silicon substrate by exposure to the oxygen atmosphere,for example, at 1100° for about one hour. The property of the siliconoxide film has been much studied in the field of semiconductors. In thesilicon oxide film, an approximately 1 nm-thick transitory layer havinga structure different from that of the bulk silicon oxide is known to bepresent close to the boundary of the silicon substrate. Thus, thesilicon oxide film of a sufficient thickness (100 nm or more) is formedin order to avoid adverse effect of this portion. Further, formation ofa thermal nitrided film is also known. A thermal nitrided film is formedon the surface of a silicon substrate by exposure to the ammoniaatmosphere, for example, at 1100° for about one hour.

The aforementioned statement also applies to the oxynitrided film andnitrided film. The ceramic film is formed from the base material, forexample, a metallic substance by thermal oxynitriding or nitriding byadjusting such conditions as the type and flow rate of gas, temperatureand time. The density (ρb) of the bulk is measured according to theaforementioned X-ray reflectivity method.

The residual stress of the ceramic film formed on the resin film ispreferably has a compressive stress of 0.01 MPa or more withoutexceeding 100 MPa.

For example, when the resin film having a ceramic film formed by thevapor deposition method, CVD method or sol-gel method is left to standunder predetermined conditions, a positive curl and negative curl occurdue to the relationship of film quality between the substrate film andceramic film. This curl is produced by the stress occurring in theceramic film. The greater the amount of curl (positive), the greaterwill be the compressive stress.

The following method is utilized to measure the internal stress of theceramic film. A ceramic film having the same composition and thicknessas those of the film to be measured is formed on a quartz substratehaving a width of 10 mm, a length of 50 mm and thickness of 0.1 mmaccording to the same procedure. The curl occurring to the sample havingbeen produced is measured by a thin film evaluation device, Model ME4000manufactured by NEC Sanei Co., Ltd., with the concave portion of thesample facing upward. Generally, the stress is said to be positive whenthe positive curl wherein the film side is contracted with respect tothe substrate by the compressive stress. Conversely, when a negativecurl is produced by the tensile stress, the stress is said to benegative.

In the present invention, the stress value is preferably 200 MPa or lessin the positive range, more preferably 0.01 MPa or more withoutexceeding 100 MPa, still more preferably 0.01 MPa or more withoutexceeding 10 MPa.

The residual stress of the resin film with the silicon oxide film formedthereon can be regulated by adjusting the degree of vacuum, for example,when the silicon oxide film is formed by vapor deposition method. FIG. 1shows the relationship between the degree of vacuum in the chamber whena 1 μm-thick silicon oxide film is formed on a quartz substrate having awidth of 10 mm, a length of 50 mm and thickness of 0.1 mm according tothe same procedure by vapor deposition, and the residual (internal)stress of the formed silicon oxide film measured by the aforementionedmethod. In FIG. 1, a laminated film having a residual stress greaterthan 0 without exceeding about 100 MPa is preferred. However, intricatecontrol is difficult in fine adjustment and adjustment cannot be madewithin this range in many cases. If the stress is too small, partialtensile stress sometimes occurs, the film will be less durable, and willbe subjected to cracks and fracture. If the stress is excessive, thefilm tends to be broken.

In the present invention, there is no particular restriction to themethod of manufacturing a ceramic film as a gas barrier film. Forexample, the ceramic film can be made by the wet type method based ofthe sol-gel technique. However, satisfactory smoothness on the molecularlevel (on the order of “nm”) cannot be easily obtained by the wet methodsuch as the spray method or spin coating method. Since a solvent isused, and the substrate (to be described later) is made of an organicmaterial, there is a restriction on the type of the substrate or solventto be used. Thus, in the present invention, the ceramic film ispreferably formed by the sputtering method, ion assist method, plasmaCVD method (to be described later), or plasma CVD method underatmospheric pressure or under the pressure close thereto (to bedescribed later). Especially the plasma CVD method under atmosphericpressure eliminates the need of using a pressure reducing chamber andprovides a high-speed and highly productive film making procedure. Whenthe gas barrier film is produced by the plasma CVD method, a filmcharacterized by a uniform and smooth surface and very small internalstress (0.01 through 100 MPa) can be produced with comparative ease.

To improve specific density ratio in the plasma method under atmosphericpressure, it is preferred to increase the output of high-frequencypower. Especially, the film production speed in the discharge space ispreferably reduced below 10 nm/sec., and the output density ispreferably 10 W/cm² or more, more preferably 15 W/cm² or more.

To perform the function of the gas barrier film, the thickness of theceramic film is preferably 5 through 2000 nm.

If the thickness is less than that, much film defect will occur and asufficient moisture resistance cannot be ensured. Theoretically, agreater thickness provides a greater moisture resistance, but ifthickness is excessive, internal stress will be increased too much andcracks will occur, with the result that excellent moisture resistancecannot be provided.

In the present invention, the ceramic film to be made into theaforementioned gas barrier layer is preferably transparent, because thetransparent gas barrier layer makes it possible to get a transparent gasbarrier film, which can be used as a transparent substrate for an ELdevice. The light transmittance of the gas barrier film is preferably80% or more, more preferably 90% or more, for example, when thewavelength of the test light is 550 nm.

The gas barrier layer obtained by the plasma CVD method, the plasma CVDmethod under atmospheric pressure or the plasma CVD method or under thepressure close thereto allows production of a ceramic film of metalliccarbide, metallic nitride, metallic oxide, metallic sulfide and others,and the mixture thereof (metallic nitride and metallic carbide nitride)to be formed as desired, by selecting such conditions as the type oforganic metallic compound as the raw material (also called thematerial), cracked gas, decomposition temperature and input power.

For example, if the silicon compound is used as a material compound andoxygen is used as a cracked gas, a silicon oxide can be produced. When azinc compound is used as a material and carbon disulfide is used as acracked gas, zinc sulfide is produced. This is because multi-phasechemical reaction is promoted at a very high speed in a plasma space dueto high-density presence of very active charged particle and activeradical in a plasma space, and the element present in the plasma spaceis converted into a thermodynamically stable compound in a very shortperiod of time.

The inorganic material can be a gas, liquid or solid at the normaltemperature and normal pressure if it contains a typical or transitionalmetal element. In the case of a gas, the material can be introduced intoa discharge space directly, but in the case of a liquid or solid, thematerial is gasified by heating, bubbling, depressurization orultrasonic irradiation. Alternatively, it can be used after beingdiluted by solvent or others. In this case, the solvent is exemplifiedby an organic solvent such as methanol, ethanol and n-hexane, or themixture thereof. These dilution solvent is decomposed into molecules andatoms in the process of plasma discharge, and its influence can bealmost ignored.

The aforementioned organic metallic compound is exemplified by such asilicon compound as silane, tetramethoxy silane, tetraethoxy silane(TEOS), tetra-n-proxy silane, tetraisoproxy silane, tetra-n-butoxysilane, tetra-t buthoxy silane, dimethyl dimethoxy silane, dimethyldiethoxy silaue, diethyl dimethoxy silane, diphenyl di-methoxy silane,methyl triethoxy silane, ethyl triethoxy silane, phenyl triethoxysilane, (3,3,3-trifluoropropyl) triethoxy silane, hexamethyl disiloxane,bis(dimethylamino)dimethyl silane, bis((dimethyl amino)methyl vinylsilane, bis(ethylamino)dimethyl silane, N,O-bis(trimethyl silyl)acetoamide, bis(trimethyl silyl) carbodiimide, diethylamino trimethylsilane, dimethylaminodimethyl silane, hexamethyl disilazane, hexamethylcyclo trisilazane, heptamethyl disilazane, nonamethyl trisilazane,octamethylcyclo tetrasilazane, tetrakis dimethylamino silane,tetraisocyanate silane, tetramethyl disilane, tris(dimethylamino)silane, triethoxy fluoro silane, alyldimethyl silane, alyltrimethylsilane, benzyltrimethyl silane, bis(trimethylsilyl)acetylene,1,4-bistrimethylsilyl-1,3-butadiene, di-t-buryl silane,1,3-disilabutane, bis(trimethylsilyl)methane, cyclopentadienyl trimethylsilane, phenyldimethyl silane, phenyltrimethyl silane, propargyltrimethyl silane, tetramethyl silane, trimethylsilyl acetylene,1-(trimethyl silyl)-1-propyne, tris(trimethylsilyl)methane,tris(trimethylsilyl) silane, vinyl trimethyl silane, hexamethyldisilane, octamethyl cyclotetrasiloxane, tetramethyl cyclotetrasiloxane,hexamethyl cyclotetrasiloxane, and M silicate 51.

The titanium compound is exemplified by titanium methoxide, titaniumethoxide, titanium isopropoxide, titanium tetraisopropoxide, titaniumn-butoxide, titanium diisopropoxide(bis-2,4-pentane dionate), titaniumdiisopropoxide(bis-2,4-ethylaceto acetate), titaniumdi-n-butoxide(bis-2,4-pentanedionate), titanium acetylacetonate, andbutyltitanate dimer.

The zirconium compound is exampled by zirconium n-propoxide, zirconiumn-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetyl acetonate, zirconium acetylacetonate, zirconium acetate, and zirconium hexaflucropentanedionate.

The aluminum compound is exemplified by aluminum ethoxide, aluminumtriisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminums-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyldialuminum tri-s-butoxide.

The boron compound is exemplified by diborane, tetraborane, boronfluoride, boron chloride, boron bromide, boron diethyl ether complex,boron-THF complex, boron-dimethyl sulfoide complex, boron diethyl ethertrifluoride complex, triethyl boron, trimethoxy boron, triethoxy boron,tri(isopropoxy)boron, borazole, trimethyl borazole, triethyl borazole,and triisopropyl borazole.

The tin compound is exemplified by tetraethyl tin, tetramethyl tin,di-n-butyl tin diacetate, tetrabutyl tin, tetraoctyl tin, tetraethoxytin, methyltriethoxy tin, diethyl diethoxy tin, triisopropyl ethoxy tin,diethyl tin, dimethyl tin, diisopropyl tin, dibutyl tin, diethoxy tin,dimethoxy tin, diisopropoxy tin, dibutoxy tin, tin dibutylate, tindiacetoacetonate, ethyl tin acetoacetonate, ethoxy tin acetoacetonate,dimethyl tin acetoacetonate, as well as tin hydrogen compound. Thehalogenated tin is exemplified by tin dichloride and tin tetrachloride.

The other organic compound is exemplified by antimony ethoxide, arsenictriethoxide, barium 2,2,6,6-tetramethyl heptanedionate, berylliumacetylacetonate, bismuth hexafluoro pentane dionate, dimethyl cadmium,calcium 2,2,6,6-tetramethyl heptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoro pentanedionate-dimethyl ethercomplex, gallium ethoxide, tetraethoxy germane, tetramethoxy germane,hafnium t-butoxide, hafnium ethoxide, indium acetyl acetonate, indium2,6-dimethyl aminoheptanedionate, ferrocene, lanthanum isopropoxide,lead acetate, lead tetraethyl, neodymium acetyl acetonate, platinumhexafluoro pentanedionate, trimethyl cyclopentadienyl platinum, rhodiumdicarbonyl acetyl acetonate, strontium 2,2,6,6-tetramethylheptanedionate, tantalum methoxide, tantalumtrifluoro ethoxide,tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide,magnesium hexafluoro acetyl acetonate, zinc acetyl acetonate, anddiethyl zinc.

The cracked gas to get the inorganic compound by decomposing thematerial gas including these metals is exemplified by hydrogen gas,methane gas, acetylene gas, carbon monoxide, carbon dioxide, nitrogengas, ammonium gas, nitrous oxide gas, nitrogen oxide gas, nitrogendioxide gas, oxygen gas, vapor, fluorine gas, hydrogen fluoride,trifluoro alcohol, trifluoro toluene, hydrogen sulfide, sulfur dioxide,carbon disulfide, and chlorine gas.

Various types of metallic carbides, metallic nitrides, metallic oxides,metallic halides and metallic sulfides can be obtained by properselection of the material gas including a metallic element and crackedgas.

A discharge gas easily converted into a plasma is added to thesereaction gases, and is fed into a plasma discharge generator.

Such a discharge gas used includes a nitrogen gas and/or Group XVIIIelement of the Periodic Table exemplified by helium, neon, argon,krypton, xenon and radon. Of these elements, nitrogen, helium, and argonare preferably used in particular. Nitrogen is more preferably becauseof low costs.

The aforementioned discharge gas and reaction gas are mixed to form agas mixture, which is supplied to plasma discharge generation apparatus(plasma generation apparatus) and form a film. The mixture ratio betweenthe discharge gas and reaction gas depends on the properties of the filmto be obtained, but the percentage of the discharge gas relative to theentire gas mixture is preferably 50% by volume or more when a reactiongas is supplied.

In the ceramic film used as a gas barrier film of the present invention,the inorganic compound contained in the ceramic film is preferablySiO_(x)C_(y) (x=1.5 to 2.0, y=0 to 0.5) or SiO_(x) SiN_(y) orSiO_(x)N_(y) (x=1 to 2, y=0.1 to 1) Especially, SiO_(x) is preferredfrom the viewpoint of gas barrier function, moisture permeability, lighttransmittance, and suitability to plasma CVD under atmospheric pressure.That the ceramic film formed by the thermal oxidation or thermalnitriding for giving ρb to be used for reference has “the samepercentage composition” as that of the ceramic film of the presentinvention signifies that the atomic percentage compositions are thesame.

In the inorganic compound included in the ceramic film of the presentinvention, for example, the film containing at least one of the oxygenand nitrogen gas, and silicon atom can be obtained by combining theoxygen gas and nitrogen gas with the aforementioned silicon compound ata predetermined ratio.

As described above, various forms of inorganic thin films can be formedby using the aforementioned material gas together with the dischargegas.

The following describes the resin film substrate used in the gas barrierfilm of the present invention.

There is no particular restriction to the film if it is made of theorganic material capable of holding the gas barrier layer having theaforementioned barrier function.

It is exemplified by a polyolefin (PO) resin including a single polymersuch as ethylene, polypropylene and butene or the copolymer thereof, anamorphous polyolefin (APO) resin such as cyclic polyolefin, a polyesterbased resin such as polyethylene terephthalate (PET), polyethylene2,6-naphthalate (PEN) and terephthalate (PET), a polyamide (PA) resinsuch as nylon 6, nylon 12 and copolymer nylon, a polyvinyl alcohol (EVA)resin, a polyvinyl alcohol resin such as ethylene vinyl alcoholcopolymer (EVOH), a polyimide (PI) resin, a polyether imide (PEI) resin,a polysulfone (PS) resin, a polyether sulfone (PES) resin, a polyetherether ketone (PEEK) resin, a polycarbonate (PC) resin, a polyvinylbutylate (PVB) resin, a polyarylate (PAR) resin, and a fluorine baseresin such as ethylene-ethylene tetrafluoride copolymer (ETFE), ethylenetrifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinylether copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVE)and perfluoro ethylene-per-fluoro propylene-per-fluoro vinyl ethercopolymer (EPA).

In addition to the aforementioned resin, it is possible to use a resincomposition made up of the acrylate compound containing a radialreactive unsaturated compound; a resin compound made up of theaforementioned acrylate compound and a mercapto compound containing athiol group; a photocurable resin such as a resin composition which isproduced by dissolving the oligomer such as epoxy acrylate, urethaneacrylate, polyester acrylate and polyether acrylate into polyfunctionalacrylate monomer; and the mixture thereof. Further, one or more of theseresins laminated by means of lamination and coating can be used as aresin film substrate.

These materials can be used independently or in combination. Thecommercially available product such as Zeronex and Zeonea (by NipponZeon Co., Ltd.), ARTON (J.S.R. Inc.) of amorphous cyclopolyolefin resinfilm, Pure Ace (by Teijin Limited) of polycarbonate film, and KonicaMinolta TAC KC4UX and KC8UX (Konica Minolta Opto Inc.) of cellulosetriacetate film can be preferable utilized.

Further, the resin film substrate is preferably transparent. When thesubstrate is transparent and the layer formed on the substrate is alsotransparent, a transparent gas barrier film can be produced. Atransparent substrate such as a organic EL device can also bemanufactured.

The resin film substrate using the aforementioned resin can be anunoriented film or an oriented film.

The resin film substrate used in the present invention can bemanufactured by the commonly known method. For example, the resin as amaterial is molten by an extruder and is extruded through an annulardies or T-dies to be quenched immediately thereafter. This procedureyields a virtually amorphous and unoriented substrate. Further, theunoriented substrate is oriented in the flow direction of the substrate(vertical axis) or in the direction perpendicular to the flow of thesubstrate (horizontal axis) by the known method of uniaxial orientation,tenter based sequential biaxial orientation, tenter based simultaneousbiaxial orientation or tubular simultaneous biaxial orientation, wherebyan oriented substrate is produced. The draw magnification in this casecan be selected properly in conformity to the resin as a material of thesubstrate, and is preferred 2 to 10 times in the vertical and horizontaldirections.

Prior to the step of vapor deposition, the resin film substrate of thepresent invention may be subjected to surface treatment such as coronaprocessing, flame processing, plasma processing, glow dischargeprocessing, surface roughing, or chemical treatment.

To enhance adhesion with the vapor deposited film, a layer of anchorcoating agent can be formed on the surface of the resin film substrateof the present invention. The anchor coating agent used for this anchorcoating agent layer can be formed by one or more of polyester resin,isocyanate resin, urethane resin, acryl resin, ethylene vinyl alcoholresin, vinyl denatured resin, epoxy resin, denatured styrene resin,denatured silicon resin, and alkyl titanate. The conventionally usedadditives can be added to these anchor coating agents. The anchorcoating agents can be coated according to the conventional method ofroll coating, gravure coating, knife coating, dip coating or spraycoating, and the solvent and dilutant are removed by drying, wherebyanchor coating is provided. The preferred amount of the anchor coatingagent is 0.1 through 5 g/m² (when dry).

The resin film substrate is preferably a long film wound in a roll. Thethickness of the film substrate differs according to the usage of thegas barrier film to be obtained, and cannot be determined simply. Whenthe gas barrier film is used for packaging, there is no particularrestriction to the thickness. From the viewpoint of adaptability topackaging purposes, the thickness is preferably 3 through 400 μm, morepreferably 6 through 30 μM.

The resin film substrate used in the present invention has a filmthickness of preferably 10 through 200 μm, more preferably 50 through100 μm.

When the gas barrier film of the present invention is used for theapplication that requires a high degree of vapor barrier function as inthe organic EL display or high-definition color liquid crystal display,the vapor transmittance is preferred not to exceed 0.001 g/m²/day asmeasured according to JIS K7129B. When this film used for the organic ELdisplay, a dark spot that grows may occur although the dark spot is verysmall. This may drastically reduce the service life of the display.Accordingly, the vapor transmittance is preferably below 1×10⁻⁵g/m²/day.

With respect to the method of manufacturing a gas barrier film of thepresent invention, the following describes the further details of theplasma CVD method and the plasma CVD method under atmospheric pressurewhich are preferably employed to form a gas barrier film or ceramicfilm:

The following describes the plasma CVD method:

In the plasma CVD method (chemical vapor deposition), a volatilized andsublimed organic metallic compound is deposited on the surface of thehigh-temperature substrate and thermal decomposition occurs, whereby athin film of thermally stable inorganic substance is formed. In thisnormal CVD method (also called thermal CVD method), the substratetemperature is required to reach 500° C. or more. Thus, this methodcannot be easily used for the production of a film for a plasticsubstrate.

On the other hand, in the plasma CVD method, electric field is appliedto the space in the vicinity of the substrate, and a space (plasmaspace) is created wherein the gas is present in the form of plasma. Thevolatilized and sublimed organic metallic compound is led into thisplasma space, and decomposition occurs. After that, the compound issprayed onto the substrate, then an inorganic thin film is formedthereon. In the plasma space, a high percentage of gas (as high asseveral percent) is ionized into iron and electron. Although gastemperature is kept low, the organic metallic compound as the materialof the inorganic film can be decomposed at a low temperature because ofvery high electron temperature and contact with the gas in the excitedstate such as an ion radical despite a low temperature. Thus, thetemperature of the substrate for manufacturing the inorganic substancecan be reduced, and a film is manufactured on the resin film substrateby this plasma CVD method.

However, the plasma CVD method requires electric field to be applied tothe gas to cause ionization so that gas is converted into plasma.Normally, a film is manufactured in the space of reduced pressureranging from 0.100 kPa through 10.1 kPa. This requires an increased sizeof the equipment and a complicated operation procedure whenmanufacturing a large-area film. Thus, this method involves aproductivity problem.

As compared with the plasma CVD method under vacuum, the plasma CVDmethod under the pressure close to the atmospheric pressure does notrequire reduction of pressure, and is characterized by higherproductivity. Not only that, since the plasma density is high, the filmmaking speed is high. As compared with the normal conditions of theplasma CVD method, the average free process of gas is very short underthe high-pressure conditions of the atmospheric pressure. This providesa very flat film which is characterized by excellent optical propertiesand excellent gas barrier function. For this reason, the plasma CVDmethod under atmospheric pressure is preferably used in the presentinvention as compared to the plasma CVD method under vacuum.

When the aforementioned ceramic film is formed on the resin film, thismethod ensures the film density and produces a thin film characterizedby superb stable performances. This method also provides stableproduction of a ceramic film having a residual stress of 0.01 MPa ormore without exceeding 100 MPa in terms of compressive stress.

FIG. 2 is a schematic diagram showing the layer structure of atransparent gas barrier film.

The gas barrier film 1 has a layer of ceramic film 3 on a resin filmsubstrate Y, e.g., polyethylene terephthalate. The gas barrier film 2includes a resin film substrate B, at least two layers of ceramic films3, and a layer 3′ containing a polymer more flexible than the ceramicfilm located between two ceramic films. The polymer layer used in thiscase is made of the material used in the resin film as the substrate ofthe gas barrier film, and the material is exemplified by;

a polyolefin (PO) resin made of an independent polymer or copolymer ofethylene, polypropylene and butene;

an amorphous polyolefin (APO) of cyclic polyolefin; and

a resin of polyethylene terephthalate and others.

There is no particular restriction if it is a film made of an organicmaterial capable of retaining the gas barrier layer.

In the gas barrier film 2, the ceramic films 3 and the layers 3′containing the polymer are shown to be alternately laminated. There isno particular restriction to their order or number in their layout ifonly a layer containing the polymer is sandwiched between the inorganiclayers.

The ceramic film of the present invention is characterized by a compactstructure and a high degree of hardness. It is preferably divided into aplurality of layers and is laminated through a stress reducing layer. Toprotect the surface, a protective layer can be provided. The stressreducing layer reduces the stress occurring to the ceramic layer andprevents cracks and other defects from occurring to the inorganicceramic film.

An adhesive layer to enhance adhesion with the resin film substrateinstead of the polymer layer, a stress reducing layer or a protectivelayer can be made of the same ceramic materials. A ceramic film havingexcellent adhesion with the resin film substrate or a less hard ceramicfilm resistant to cracks and damage can be obtained by selecting theceramic film forming conditions (reaction gas, electric power andhigh-frequency power source) and changing the percentage of carboncontent, for example.

The aforementioned gas barrier films of the present invention can beused as various forms of sealing materials and films.

The aforementioned gas barrier film of the present invention can bepreferably used in the display element, for example, organic EL device.When used in the organic EL device, the gas barrier film of the presentinvention can be used as a substrate to take in light through this filmsince the gas barrier film is transparent. To be more specific, atransparent conductive thin film such as ITO is provided as atransparent electrode on this gas barrier film, and a resin substratefor organic electroluminescent device is manufactured. Then an organicEL material layer including the light emitting layer is provided on theITO transparent conductive film on the substrate used as an anode, and acathode made up of a metallic film is formed, whereby an organic ELdevice is formed. Another sealing material (or the same one) is placedon this organic EL device, and the gas barrier film substrate is bondedthe surrounding area so as to enclose and seal the device. Thus, theorganic EL device layer can be sealed. This arrangement protects againstadverse effect of the external moisture or gases such as oxygen upon thedevice.

The transparent conductive film can be formed by the vacuum vapordeposition method or sputtering method, as well as by the coating methodincluding a sol-gel method using the metallic alkoxide such as indium ortin. Such a method will provide an ITO film characterized by excellentconductivity on the level of a specific resistance value of 10⁻⁴Ω·cm.This film is preferably manufactured according to the plasma CVD methodusing an organic metallic compound as exemplified by the metallicalkoxide such as indium or tin or alkyl metal, in the same manner asabove. This will be discussed later.

The details of the organic EL device layer will also be described later.The device having a light emitting layer of phosphorescent typecontaining the phosphorescent dopant on the light emitting layerexhibits excellent light emission efficiency as an organic EL device inthe present invention, and is preferably used.

The following describes the method of manufacturing the gas barrier filmusing the plasma CVD method under atmospheric pressure or under thepressure close thereto.

Referring to FIGS. 3 through 6, the following describes an example ofthe plasma film manufacturing apparatus used in the production of thegas barrier film in the present invention. In the drawing, symbol Fdenotes a longer film as an example of the substrate.

In the plasma discharge processing apparatus shown in FIGS. 3 and 4, thematerial gas including the aforementioned metal and the cracked gas areproperly selected from a gas supply unit. The discharge gas easilyconvertible into plasma is mixed with these reaction gases, and the gasis fed into the plasma discharge generation apparatus, whereby theaforementioned ceramic film can be produced.

As described above, such a discharge gas includes a nitrogen gas and/orGroup XVIII element of the Periodic Table exemplified by helium, neon,argon, krypton, xenon and radon.

Of these elements, nitrogen, helium, and argon are preferably used inparticular. Nitrogen is more preferably because of low costs.

FIG. 3 shows an atmospheric plasma discharge processing apparatus. Itcontains a gas supply unit and electrode temperature regulating unit(not illustrated in FIG. 3, but shown in FIG. 4), in addition to theatmospheric plasma discharge processing apparatus and an electric fieldapplication unit having two power sources.

The plasma discharge processing apparatus 10 has the opposing electrodesformed of a first electrode 11 and second electrode 12. From the firstelectrode 11, the first high-frequency electric field of frequency ω1,electric field intensity V₁ and current I₁ from the first power source21 is applied between the opposing electrodes. From the second electrode12, the second high-frequency electric field of frequency ω2, electricfield intensity V₂ and current I₂ from the second power source 22 isapplied between the opposing electrodes. The first power source 21 canapply high frequency field intensity (V₁>V₂) higher than that of thesecond power source 22. Further, the frequency ω1 of the first powersource 21 can apply the frequency lower than the second frequency ω2 ofthe second power source 22.

The first filter 23 is installed between the first electrode 11 andfirst power source 21, and is intended to facilitate the flow of currentfrom the first power source 21 to the first electrode 11. The currentfrom the second power source 22 is grounded so as to hinder the flow ofcurrent from the second power source 22 to the first power source 21.

The second filter 24 is installed between the second electrode 12 andsecond power source 22, and is intended to facilitate the flow ofcurrent from the second power source 22 to the second electrode. Thecurrent from the first power source 21 is grounded so as to hinder theflow of current from the first power source 21 to the second powersource 21.

Gas G is fed between the opposing electrodes of the first electrode 11and second electrode 12 (discharge space) from the gas supply unit asshown in FIG. 4 (to be described later), and high frequency electricfield is applied from the first electrode 11 and second electrode 12 tocause discharge processing. The gas G made in the state of plasma issprayed and jetted to the lower side of the opposing electrodes (to thebottom side of paper surface), so that the processing space formed bythe bottom surface of the opposing electrodes and the substrate F isfilled with the gas G in the state of plasma. Close to the processingposition 14, a thin film is formed on the substrate F unwound and fedfrom the unwinder of the substrate (not illustrated) or the substrate Ffed from the preceding process. During the formation of the thin film,the electrode is heated or cooled by a medium coming from the electrodetemperature regulating unit as shown in the FIG. 4 (to be describedlater) through the tube. Depending on the temperature of the substrateduring the plasma discharge, the physical properties and composition ofthe thin film to be obtained may vary. This is preferably provided withadequate control. Such an insulating material as distilled water or oilis preferably used as the medium for temperature regulation. At the timeof plasma discharge processing, the temperature inside the electrode ispreferably regulated to ensure uniform temperature in order to minimizeuneven temperature of the substrate both across the width and along thelength.

A plurality of jet type atmospheric pressure plasma discharge processingapparatuses are arranged in contact with each other in series, and thegas in the same state of plasma can be discharged simultaneously. Thisallows repeated high-speed processing operations. A laminated thin filmhaving different layers can be formed when gases in a different state ofplasma are jetted from these apparatuses.

FIG. 4 is a schematic diagram showing an example of the atmosphericpressure plasma discharge processing apparatuses wherein a substance isprocessed between the opposing electrodes preferably used in the presentinvention.

The atmospheric pressure plasma discharge processing apparatuses of thepresent invention includes at least a plasma discharge processingapparatus 30, an electric field applying unit 40 having two powersources, a gas supply unit 50 and an electrode temperature regulatingunit 60.

FIG. 4 shows that a thin film is formed by plasma discharge processingof a substrate F, using the opposing electrodes (discharge processingspace) 32 of a roll rotating electrode (first electrode) 35 and arectangular stationary electrode group (second electrode) 36.

For the opposing electrodes (discharge processing space) 32 of a rollrotating electrode (first electrode) 35 and a rectangular stationaryelectrode group (second electrode) 36, the first high frequency electricfield of frequency ω1, electric field intensity V₁ and current I₁ isapplied from the first power source 41 to the roll rotating electrode(first electrode) 35, while the second high frequency electric field offrequency ω2, electric field intensity V₂ and current I₂ is applied fromthe second power source 42 to the rectangular stationary electrode group(second electrode) 36.

The first filter 43 is installed between the roll rotating electrode(first electrode) 35 and first power source 41, and is intended tofacilitate the flow of current from the first power source 41 to thefirst electrode. The current from the second power source 42 is groundedso as to hinder the flow of current from the second power source 42 tothe first power source. The second filter 44 is installed between therectangular stationary electrode group (second electrode) 36 and secondpower source 42, and is intended to facilitate the flow of current fromthe second power source 42 to the second electrode. The current from thefirst power source 41 is grounded so as to hinder the flow of currentfrom the first power source 41 to the second power source.

In the present invention, the roll rotating electrode 35 can be used asthe second electrode, and the rectangular stationary electrode group 36as the first electrode. The first power source is connected to the firstelectrode, and the second power source is connected to the secondelectrode. The high frequency electric field higher than that of thesecond power source (V₁>V₂) is preferably applied to the first powersource. Further, the frequency has the capacity represented by ω1<ω2.

The current is preferably I₁<I₂. The current I₁ of the first highfrequency electric field is preferably 0.3 mA/cm² through 20 mA/cm²,more preferably 1.0 mA/cm² through 20 mA/cm². The current I₂ of thesecond high frequency electric field is preferably 10 mA/cm² through 100mA/cm², more preferably 20 mA/cm² through 100 mA/cm².

After the flow rate has been controlled, the gas G generated from thegas generating apparatus 51 of the gas supply unit 50 is fed to a plasmadischarge processing container 31 from the gas inlet 52.

The substrate F is unwound and fed from the unwinder of the substrate(not illustrated) or is fed from the preceding process. It passesthrough the guide roll 64, and the air entrained by the substrate is cutoff by the nip roll 65. The substrate F is wound and rotated while beingkept in contact with the roll rotating electrode 35, and is conveyed tothe position between roll rotating electrode 35 and the rectangularstationary electrode group 36. Electric field is applied from both theroll rotating electrode (first electrode) 35 and the rectangularstationary electrode group (second electrode) 36, and discharged plasmais generated by the opposing electrodes (discharge processing space) 32.The substrate F is wound and rotated in contact with the roll rotatingelectrode 35 and a thin film is formed by the gas in the state ofplasma. Having passed through the nip roll 66 and guide roll 67, thesubstrate F is wound by a winder (not illustrated) or is fed to the nextprocess.

The processed exhaust gas G′ having been discharged is ejected from anexhaust outlet 53.

To heat or cool the roll rotating electrode (first electrode) 35 andrectangular stationary electrode group (second electrode) 36 during theformation of a thin film, the medium whose temperature has beenregulated by the electrode temperature regulating unit 60 is sent toboth electrodes by a pump P through a tube 61 so that the temperature isregulated from inside the electrodes. The reference numerals 68 and 69denote partition plates for separating the plasma discharge processingcontainer 31 from the outside.

FIG. 5 is a perspective view representing an example of the structuresof the conductive metallic base material of the roll rotating electrodeof FIG. 4 and the dielectric covering the same from above.

In FIG. 5, the roll electrode 35 a is made of a conductive metallic basematerial 35A and the dielectric 35B covering the same from above. Amedium for temperature regulation (water or silicone oil) is circulatedto control the electrode surface temperature during plasma dischargeprocessing.

FIG. 6 is a perspective view representing an example of the structure ofthe conductive metallic base material of a rectangular electrode and thedielectric covering the same.

In FIG. 6, the rectangular electrode 36 a is made of a conductivemetallic base material 36A covered by the dielectric 36B. Theaforementioned electrode is formed as a metallic pipe, which served as ajacket to adjust the temperature for electric discharge processing.

A plurality of rectangular stationary electrodes are arranged on thecircumference larger than that of the aforementioned roll electrode. Thedischarge area of the aforementioned electrode is expressed by the sumof the areas on the surface of all the rectangular stationary electrodesarranged face to face with the roll rotating electrode 35.

The rectangular electrode 36 a of FIG. 6 can be a cylindrical electrode.As compared with the cylindrical electrode, the rectangular electrodehas the effect of expanding the range of electric discharge range(discharge area), and therefore, it is preferably used in the presentinvention.

In FIGS. 5 and 6, after ceramics as dielectrics 35B and 36B are sprayedonto the conductive metallic base materials 35A and 36A respectively,the roll electrode 35 a and rectangular electrode 36 a are provided withpore sealing, using the pore sealing material of inorganic compound. Thecovering of the ceramic dielectric should be about 1 mm thick on oneside. Alumina and silicon nitride are preferably used as the ceramicmaterial to be sprayed. In particular, alumina is more preferably usedsince it can be easily processed. The dielectric layer can be adielectric provided with lining treatment wherein inorganic material isarranged by lining.

The conductive metallic base materials 35A and 36A are exemplified bysuch a metal as a titanium metal or titanium alloy, silver, platinum,stainless steel, aluminum and iron, a composite material between ironand ceramic, and a composite material between aluminum and ceramic. Thetitanium metal or titanium alloy is preferred in particular for thereasons to be discussed later.

The distance between the opposing first and second electrodes is definedas the minimum distance between the aforementioned dielectric surfaceand the conductive metallic base material surface of the otherelectrode, when one of the electrodes is provided with a dielectric.When both electrodes are provided with dielectrics, it is defined as theminimum distance between dielectric surfaces. The distance betweenelectrodes is determined by giving consideration to the thickness of thedielectric provided on the conductive metallic base material, theintensity of the electric field to be applied, and the object of usingplasma. In any case, to ensure uniform electric discharge, this distanceis preferably 0.1 through 20 mm, more preferably 0.2 through 2 mm.

The details of the conductive metallic base material and dielectricpreferably used in the present invention will be described later.

The Pyrex (registered trademark) glass-made processing container ispreferably used as the plasma discharge processing container 31. Ifinsulation with the electrode is provided, a metallic product can alsobe used. For example, the inner surface of the aluminum or stainlesssteel frame may be lined with a polyimide resin. The aforementionedmetal frame may be sprayed with ceramic to provide insulation. In FIG.2, both sides of the two parallel electrodes (up to close to thesubstrate surface) are preferably covered with the aforementionedmaterial.

The following commercially available products can be used as the firstpower source (high frequency power source) installed on the atmosphericpressure plasma discharge processing apparatus of the present invention:

Power Source for Application Manufacturer Frequency Product Name

A1 Shinko Electric 3 kHz SPG3-4500

A2 Shinko Electric 5 kHz SPG5-4500

A3 Kasuga Electric 15 kHz AGI-023

A4 Shinko Electric 50 kHz SPG50-4500

A5 Heiden Research Laboratory 100 kHz*PHF-6 k

A6 Pearl Industry 200 kHz CF-2000-200 k

A7 Pearl Industry 400 kHz CF-2000-400 k

The following commercially available products can be used as the secondpower source (high frequency power source):

Power Source for Application Manufacturer Frequency Product Name

B1 Pearl Industry 800 kHz CF-2000-800 k

B2 Pearl Industry 2 MHz CF-2000-2M

B3 Pearl Industry 13.56 MHz CF-5000-13M

B4 Pearl Industry 27 MHz CF-2000-27M

B5 Pearl Industry 150 MHz CF-2000-150M

Any of them can be used preferably.

Of the aforementioned power sources, the ones marked with an asteriskindicate an impulse high frequency power source (100 kHz in thecontinuous mode) manufactured by Heiden Research Laboratory. Others arehigh frequency power sources capable of applying only the continuoussinusoidal wave.

In the present invention, the atmospheric pressure plasma dischargeprocessing apparatus is preferred to use the electrode capable ofmaintaining the state of uniform and stable electric discharging byapplication of the aforementioned electric field.

In the present invention, for the electric power to be applied betweenthe opposing electrodes of the present invention, an electric power(output density) of 1 W/cm² or more is supplied to the second electrode(second high-frequency electric field). Then the electrical dischargegas is excited to generate plasma and to afford energy to a thin filmforming gas, whereby a thin film is formed. The upper limit value ofelectric power supplied to the second electrode is preferably 50 W/cm²,more preferably 20 W/cm². The lowest limit value is preferably 1.2W/cm². It should be noted, however, that discharge area (cm²) refers tothe area in the range wherein electric discharging occurs between theelectrodes.

When an electric power (output density) of 1 W/cm² or more is applied tothe first electrode (first high-frequency electric field), the outputdensity can be improved with the second high-frequency electric fieldkept uniform. This arrangement generates further uniform andhigh-density plasma and ensures compatibility between a further increasein the film making speed and further improvement of the film quality.The electric power is preferably 5 W/cm² or more. The upper limit valueof the electric power supplied to the first electrode is preferably 50W/cm².

There is no particular restriction to the waveform of the high-frequencyelectric field. There are a continuous sinusoidal wave-like continuousoscillation mode called a continuous mode, and a continuous oscillationmode for performing intermittent ON/OFF operations called a pulse mode.Either of them can be used. The continuous sinusoidal wave is preferablyused at least on the second electrode (second high-frequency electricfield) in order to produce a more compact and high-quality film.

The electrode used in the thin film forming method based on atmosphericpressure plasma described above is required to meet severe workingconditions both in structure and performance. To meet this requirement,an electrode is preferably made of the metallic base material coveredwith a dielectric.

The dielectric-covered electrode used in the present invention isrequired to have characteristics conforming to various forms of metallicbase materials and dielectrics.

One of these characteristics is such a combination that ensures thedifference in the linear thermal coefficient of expansion between themetallic base material and dielectric is 10×10⁻⁶/° C. or less. Thisdifference is preferably 8×10⁻⁶/° C. or less, more preferably 5×10⁻⁶/°C. or less, still more preferably 2×10⁻⁶/° C. or less. The linearthermal coefficient of expansion in the sense in which it is used hererefers to the physical properties specific to a known material.

The following shows combinations between the conductive metallic basematerials and dielectrics wherein the difference in the linear thermalcoefficient of expansion is kept within the aforementioned range:

1: The metallic base material is made of pure titanium or titaniumalloy, and the dielectric is made of ceramic sprayed coating.

2: The metallic base material is made of pure titanium or titaniumalloy, and the dielectric is made of glass lining.

3: The metallic base material is made of stainless steel, and thedielectric is made of ceramic sprayed coating.

4: The metallic base material is made of stainless steel and thedielectric is made of glass lining.

5: The metallic base material is made of a composite material of ceramicand iron, and the dielectric is made of ceramic sprayed coating.

6: The metallic base material is made of a composite material of ceramicand iron, and the dielectric is made of glass lining.

7: The metallic base material is made of a composite material of ceramicand aluminum, and the dielectric is made of ceramic sprayed coating.

8: The metallic base material is made of a composite material of ceramicand aluminum, and the dielectric is made of glass lining.

From the viewpoint of the difference in linear thermal coefficient ofexpansion, the aforementioned items 1 or 2 and 5 through 8 arepreferably used. Item 1 is preferably used in particular.

In the present invention, from the viewpoint of the aforementionedcharacteristics, titanium or titanium alloy is preferably used inparticular as the metallic base material. When the titanium or titaniumalloy is used as the metallic base material, and the aforementionedmaterial is used as the dielectric, it is possible to ensure a long-timeuse under severe conditions, free from deterioration of the electrode,cracks, peeling, disengagement or other defects during use.

The atmospheric pressure plasma discharge processing apparatusapplicable to the present invention is exampled by the atmosphericpressure plasma discharge processing apparatuses disclosed in theUnexamined Japanese Patent Application Publication No. 2004-68143, theUnexamined Japanese Patent Application Publication No. 2003-49272, andInternational Patent 02/48428, in addition to the apparatuses discussedabove,

The following describes the transparent conductive film provided on thesubstrate of an organic EL device.

The transparent conductive film of the ITO film or the like can beproduced by the vapor deposition method, plasma CVD method, or plasmaCVD method under atmospheric pressure or under the pressure closethereto.

The sol-gel method (coating method) can also be used to product thisfilm.

However, the plasma CVD method under atmospheric pressure is preferablyused to produce the aforementioned film. For example, from an industrialviewpoint, the ITO film characterized by excellent conductivityequivalent to a specific resistance of about 10⁻⁴Ω can be produced usinga DC magnetron sputtering apparatus. In the aforementioned physicalmanufacturing method (PVD method), target objects are deposited on asubstrate in the gas phase so that a film is grown. Since vacuumcontainer is used, this method involves the need of using a costlylarge-scale apparatus, poor efficiency in material use and poorproductivity. Further, this method is not suited for formation of a filmof large area. What is more, in order to ensure a product of lowresistance, temperature must be increased to 200 through 300° C. at thetime of film production. Thus, this method has been unsuitable tomanufacture a transparent conductive film of low resistance with respectto the plastic film.

The gas used in the formation of a transparent conductive film differsaccording to the type of the transparent conductive film arranged on thesubstrate. Basically, it is a gas mixture of inert gas and reaction gasconverted into plasma for formation of the transparent conductive film,similarly to the case of the above. The inert gas includes the GroupXVIII elements of the Periodic Table such as helium, neon, argon,krypton, xenon and radon as well as nitrogen gas, similarly to the caseof the above. Argon and helium are preferably used in particular. Aplurality of reaction gases can be used in the present invention. Inthis case, at least one of them is converted into plasma in thedischarge space, and the components for forming the transparentconductive film are contained therein. Although there is no particularrestriction to such gases, an organic metallic compound is preferablyused. No restriction is imposed of the type of the organic metalliccompound, but the organic metallic compound containing oxygen in themolecule is preferred. The substances preferred in particular areorganic metallic compounds such as β diketone metal complex, metallicalkoxide and alkyl metal. More preferably used are the reaction gasesmade up of the compound selected from such compounds as indiumhexafluoro pentane dionate, indium methyl(trimethyl)acetyl acetate,indium acetyl acetonate, indium isopropoxide, indium trifluoro pentanedionate, tris(2,2,6,6-tetramethyl 3,5-heptane dionate)indium,di-n-butylbis(2,4-pentane dionate)tin, di-n-butyl diacetoxy tin,di-t-butyl diacetoxy tin, tetraisopropoxy tin, tetrabutoxy tin, and zincacetyl acetonate.

Of these, particularly preferred substances are indium acetyl acetonate,tris(2,2,6,6-tetramethyl 3,5-heptane dionate)indium, zinc acetylacetonate and di-n-butyl diacetoxy tin. These organic metallic compoundsare available on the market. For example, indium acetyl acetonate can beprocured easily from Tokyo Chemical Industry Co., Ltd.

In the formation of the conductive film, in addition to the organicmetallic compounds containing one or more oxygen atoms in thesemolecules, the gas used for doping for the purpose of improvingconductivity can be used. The reaction gas used for doping isexemplified by aluminum isopropoxide, nickel acetyl acetonate, manganeseacetyl acetonate, boron isopropoxide, n-butoxy antimony, tri-n-butylantimony, di-n-butyl bis(2,4-pentane dionate)tin, di-n-butyl diacetoxytin, di-t-butyl diacetoxy tin, tetraisopropoxy tin, tetrabutoxy tin,tetrabutyl tin, zinc acetyl acetonate, propylene hexafluoride,cyclobutane octofluoride and methane tetrafluoride.

Further, in addition to the reaction gas containing the components ofthe transparent conductive film, water can be used as a reaction gas,whereby transparent conductive film characterized by excellentconductivity and etching speed can be produced. The amount of wateradded to the reaction gas is preferably 0.0001% by volume through 10% byvolume, more preferably 0.001 through 1% by volume, in the gas mixturebetween the reaction gas and inert gas.

The reaction gas of the present invention that can be used in thepresent invention can be exemplified by the organic metallic compoundincluding the elements constituting the transparent conductive film, andwater, oxidizing substance such as oxygen, reducing gas such ashydrogen, nitrogen monoxide, nitrogen dioxide, carbon monoxide andcarbon dioxide.

The quantitative ratio of the reaction gas used as the major componentof the transparent conductive film relative to the reaction gas used ina small quantity for the purpose of doping varies according to the typeof the transparent conductive film to be formed. For example, in the ITOfilm obtained by doping tin into the indium oxide, the amount of thereaction gas is adjusted so that the ratio of the number of In atomsrelative to that of Sn atoms in the ITO film obtained will be 100:0.1through 100:15. The ratio of the number of In atoms relative to that ofSn atoms can be obtained from the XPS measurement. In the transparentconductive film (also called FTO film) obtained by doping fluorine intotin oxide, the amount of the reaction gas is adjusted so that the ratioof the number of Sn atoms relative to that of F atoms in the FTO filmobtained will be 100:0.01 through 100:50. The ratio of the number of Snatoms relative to that of F atoms can be obtained from the XPSmeasurement. In the In₂O₃—ZnO based amorphous transparent conductivefilm, the amount of the reaction gas is adjusted so that the ratio ofthe number of the In atoms relative to that of Zn atoms will be 100:50through 100:5. The ratio of the number of In atoms relative to that ofZn atoms can be obtained from the XPS measurement.

The reaction gas is available in two types; the reaction gas used as themajor component of the transparent conductive film, and the reaction gasused in a small quantity for the purpose of doping. Further, in thepresent invention, the metallic element as the major component of thetransparent conductive film, the metallic element for doping, andsilicon are also introduced. There is no particular restriction to themethod of introducing the silicon. When a transparent conductive film isformed, reaction gas can be added in order to adjust the resistance ofthe transparent conductive film. The reaction gas preferably used toadjust the resistance of the transparent conductive film is exemplifiedby an organic metallic compound, especially β diketone metal complex,metallic alkoxide and alkyl metal. To put it more specifically, thesilicon compound is exemplified by tetramethoxy silane, tetraethoxysilane, tetra-iso-propoxy silane, tetra-n-propoxy silane, tetra-n-butoxysilane, tetra-sec-butoxy silane, tetra-tert-butoxy silane,tetra-penta-ethoxy silane, tetra-penta-iso-propoxy silane,tetra-penta-n-propoxy silane, tetra-penta-sec-butoxy silane,tetra-penta-tert-butoxy silane, methyl trimethoxy silane, methyltriethoxy silane, methyl tripropoxy silane, methyl tributhoxy silane,dimethyl dimethoxy silane, dimethyl ethoxy silane, dimethyl methoxysilane, dimethyl propoxy silane, dimethyl buthoxy silane, methyldimethoxy silane, methyl diethoxy silane, and hexyl trimethoxy silane.Of these, tetraethoxy silane is preferably used.

The thickness of the transparent conductive film is preferably 0.1 nmthrough 1000 nm.

After having been formed under the pressure close to the atmosphericpressure, the transparent conductive film can be heated to adjust thecharacteristics of the transparent conductive film. The amount ofhydrogen in the film can be changed by this heat treatment. Thetemperature for heat treatment is preferably 50 through 300° C., morepreferably 100 through 200° C. There is no particular restriction to theatmosphere of heating. Any proper atmosphere can be selected from amongair atmosphere, reducing atmosphere including the reducing gas such ashydrogen, oxidizing atmosphere including oxidizing gas such as oxygen,vacuum and inert gas atmosphere. When the reducing and oxidizingatmospheres are adopted, it is preferred to use the reducing andoxidizing gases diluted by a rare gas or nitrogen. In this case, theconcentration of the reducing and oxidizing gases is preferably 0.01through 5% by volume, more preferably 0.1 through 3% by volume.

The transparent conductive film obtained by the transparent conductivefilm forming method of the present invention may contain carbon sinceorganic metallic compound is used as a reaction gas. In this case, theamount of the carbon contained therein is preferably 0 through 5.0, morepreferably 0.01 through 3, in terms of the concentration in the numberof atoms.

In the present invention, the aforementioned ceramic film or transparentconductive film is formed under the pressure close to the atmosphericpressure, but there is no particular restriction to the temperature ofthe substrate used in this case. When glass is used as a substrate, thistemperature is preferably 300° C. or more. When the polymer (to bedescribed later) is used this temperature is preferably 200° C. or more.

The following describes the organic EL device using the aforementionedgas barrier film and a resin substrate for organic EL device with thetransparent conductive film formed on the gas barrier film:

(Sealing Film and its Manufacturing Method)

The present invention is partly characterized in that the gas barrierfilm having the aforementioned ceramic film is used as a substrate.

In the gas barrier film having the aforementioned ceramic film, atransparent conductive film is further formed on the ceramic film. Thisis used as an anode, and an organic EL material layer for correcting theorganic EL device, and a metallic layer as a cathode are laminated onthis anode. Further, another gas barrier film as a sealing film isbonded thereon, whereby sealing is provided.

The gas barrier film having a ceramic film of compact structure of thepresent invention can be used as another sealing material (sealingfilm). Further, for example, it is possible to use as a sealing film thecommonly known gas barrier film used for packaging, as exemplified bythe film with silicone oxide or aluminum oxide vapor-deposited on aplastic film, or a gas barrier film with a compact ceramic layer and aimpact reducing polymer layer of superb flexibility alternatelylaminated thereon. Although it cannot be used as a gas barrier film onthe lighting side, the resin laminated metal foil (polymer film) inparticular is a low-cost sealing material of low moisture permeability,and can be used preferably as a sealing film when it is not intended forlighting purposes (when transparency is not required).

In the present invention, unlike the metallic thin film formed bysputtering or vapor deposition, or the conductive film made of theliquid electrode material such as a conductive paste, the metal foilrefers to the metal foil or film formed by rolling operation.

There is no particular restriction to the metal foil, which isexemplified by a copper (CU) foil, aluminum (Al) foil, gold (Au) foil,brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy,stainless steel foil, tin (Sn) foil and high-nickel allow foil.

The thickness of the metal foil is preferably 6 through 50 μm. If it isbelow 6 μm, a pin hole may be created at the time of use, depending onthe type of the material used for the metal foil, and the requiredbarrier function (moisture permeability, oxygen permeability) cannot beobtained in some cases. If the thickness is over 50 μm, the productioncost may be increased, depending on the type of the material used forthe metal foil, or the thickness of the organic EL device may beincreased, with the result that the advantages of the film cannot beprovided in some cases.

In the metal foil with the resin film (polymer foil) laminated thereon,various materials disclosed in the “New Development in the FunctionalPackaging Materials” (Toray Research Center) can be used as a resinfilm. Examples are polyethylene resin, polypropylene resin, polyethyleneterephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymerresin, ethylene-vinyl acetate copolymer resin, acrylonitryl-butadienecopolymer resin, cellophane resin, vinylon resin, and polyvinylidenechloride. The polypropylene resin and nylon resin can be drawn, or canbe coated with the polyvinylidene chloride resin. The polyethylene resinof either low density or high density can be utilized.

Of the aforementioned high polymer materials, nylon (Ny), nylon (KNy)coated with vinylidene chloride (PVDC), unoriented polypropylene (CPP),oriented polypropylene (OPP), polypropylene (KOP) coated with the PVDC,polyethylene terephthalate (PET), cellophane (KPT) coated with the PVDC,polyethylene-vinyl alcohol copolymer (Eval), low-density polyethylene(LDPE), high-density polyethylene (HDPE), and linear low-densitypolyethylene (LLDPE) can be employed. Needless to say, a multilayer filmformed by co-extrusion with a different type of film as required and amultilayer film laminated by changing the drawing angle can be used asthese thermoplastic films. It is naturally possible to create the filmby a combination of the distributions of the density and molecularweight of the film used to ensure the required physical properties ofthe packaging material.

The thickness of the polymer film cannot be regulated indiscriminately.It is preferably 3 through 400 μm, more preferably 10 through 200 μm,still more preferably 10 through 50 μm.

A generally used laminating machine can be used to coat (laminate) thepolymer film on one surface of the metal foil. A polyurethane,polyester, epoxy or acryl based adhesive can be utilized. A curing agentcan be used as required. The dry lamination method, hot melt laminationmethod and extrusion lamination method can be employed. Use of the drylamination method is preferred.

The film coated with polymer film on one surface of the metal foil iscommercially available for use in packaging materials. For example, thedry lamination film having a structure of an adhesive layer, aluminumfilm (9 μm) and polyethylene terephthalate (PET, 38 μm) (two-partadhesive type urethane based adhesive having a thickness of 1.5 μm asthe adhesive layer) is available on the market. This film can be used toseal the cathode side of the organic EL device.

As will be described later, two films are preferably sealed by themethod of laminating a commonly used impulse sealer thermal fusing typeresin layer and fusing with the impulse sealer. In this case, when gasbarrier films are sealed with each other, film handling difficultieswill arise at the time of sealing operation if film thickness exceeds300 μm. Further, thermal fusing difficulties due to the impulse sealerand other factors will arise. To avoid this, the film thickness ispreferably kept not to exceed 300 μm.

[Sealing of Organic EL Device]

After each layer of the organic EL device has been formed on the resinsubstrate for organic EL device with a transparent conductive filmformed on the resin film having the aforementioned ceramic film of thepresent invention, the surface coated with the ceramic film seals theorganic EL device so as to cover the cathode surface under theenvironment wherein air was purged by an inert gas, using theaforementioned sealing film.

Helium or argon in addition to nitrogen is preferably used as the inertgas. The rare gas made up of a mixture of helium and argon is alsopreferably used. The percentage of the inert gas in the entire gas ispreferably 90 through 99.9% by volume.

Storage stability is improved by sealing under the environment whereinpurging is conducted by an inert gas.

It is important that the ceramic film surface of the sealing film shouldbe bonded on the cathode of the organic EL device. If the polymer filmsurface of the sealing film is bonded on the cathode of the organic ELdevice, partial conduction or electrolytic corrosion may occur asdescribed above. This may further lead to occurrence of a dark spot.

In one of the method for bonding the sealing film on the cathode of theorganic EL device, the resin films that can be fusion-bonded by thecommonly used impulse sealer, as exemplified by a vinyl ethylene acetatecopolymer (EVA) film, polypropylene (PP) film or polyethylene (PE) film,are laminated, and are fuse-bonded by impulse sealer, wherein sealing isprovided.

Dry lamination method is preferable for this bonding from the viewpointof workability. In this method, an adhesive layer having a curingproperty of about 1.0 through 2.5 μm is generally used. However, if theexcessive amount of the adhesive is coated, a tunnel, oozing out or finewrinkles occur. Accordingly, the amount of adhesive is preferably 3through 5 μm in terms of dried film thickness.

The hot melt lamination method refers to a method of melting the hotmelt adhesive and coating an adhesive layer on the substrate, whereinthe thickness of the adhesive layer generally can be set over a widerange from 1 through 50 μm. EVA, EEA, polyethylene, butyl rubber or thelike is used as the base resin of the hot melt adhesive generally used.Rosin, xylylene resin, terpene resin or styrene resin is added as atackifier, and wax or the like is added as a plasticizer.

Extrusion lamination method refers to the method of coating thesubstrate with the resin melted at a high temperature by means of dies.The thickness of the resin layer can be generally set over a wide rangefrom 10 through 50 μm.

LDPE, EVA, PP or the like is generally used as the resin used forextrusion lamination.

FIG. 7 is a schematic view showing the cross section representing theorganic EL device sealed by the step wherein, after each layer of theorganic EL device has been formed on the gas barrier film of the presentinvention, the resin laminated aluminum foil with silicon oxide, and theaforementioned gas barrier film are further bonded.

In FIG. 7, an organic EL device containing an anode (ITO) 4, each layer5 of the organic EL device including the light emitting layer and acathode (e.g., aluminum) 6 formed thereon is formed on the gas barrierfilm 1 having a ceramic film 3 of the present invention formed on theresin film substrate Y. Further, another sealing film 2 is placed on thecathode and the position around the substrate film is bonded, wherebythe organic EL device including the organic EL material layer is sealed.In the sealing film 2, the ceramic film 3 is formed on the metal(aluminum) foil 7 and the resin layer 8 is laminated on the sideopposite the metal foil, wherein the sealing film 2 is bonded so as tocontact the side of the ceramic film 3.

The following describes the each layer of the organic EL material(constituent layer):

[Organic EL Device]

The following describes the details of the constituent layer of theorganic EL device of the present invention. The following describes thepreferred examples of the structure of the organic EL device layer,without the present invention being restricted thereto.

(1) Anode/light emitting layer/electron transport layer/cathode

(2) Anode/positive hole transport layer/light emitting layer/electrontransport layer/cathode

(3) Anode/positive hole transport layer/light emitting layer/electrontransport layer/cathode

(4) Anode/positive hole transport layer/light emitting layer/electrontransport layer/cathode buffer layer/cathode

(5) Anode/anode buffer layer/positive hole transport layer/lightemitting layer/positive hole blocking layer/electron transportlayer/cathode buffer layer/cathode

(Anode)

The anode of the organic EL device preferably used is the one wherein ametal having a greater work function (4 eV or more), alloy, electricallyconductive compound, or the mixture thereof is used as an electrodesubstance. Such an electrode substance is a conductive transparentmaterial exemplified by a metal such as gold, CuI, indium tin oxide(ITO), SnO₂ or ZnO. It is also possible use the material that can beused to produce a amorphous transparent conductive film of IDIXO(In₂O₃—ZnO) or the like. In the anode, a thin film has been formed onthese electrode substances by vapor deposition or sputtering method anda desired shape pattern is formed by photolithography. Alternatively,when a high pattern accuracy is not required (about 100 μm or more), apattern can be formed by means of a mask having a desired shape patternat the time of the vapor deposition or sputtering of the aforementionedsubstance. When picking up the light emitted from this anode, thetransmittance is preferably greater than 10%. The sheet resistance asthe anode is preferably a few hundred Ω/

or less. The film thickness is preferably 10 through 1000 nm, morepreferably 10 through 200 nm, although it may differ according to thetype of the material.

(Cathode)

In the meantime, the cathode of the organic EL device preferably used isthe one wherein a metal having a smaller work function (4 eV or less)(called an electron injection type metal), alloy, electricallyconductive compound, or the mixture thereof is used as an electrodesubstance. Such an electrode substance is exemplified by sodium,sodium-cadmium alloy, magnesium, lithium, magnesium/copper mixture,magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indiummixture, aluminum/aluminum oxide (Al₂O₃) mixture, indium,lithium/aluminum mixture, and rare-earth metal. Of these substances, amixture between the electron injection type metal and the second metalas a stable metal having a greater work function thereby is preferablyutilized from the viewpoint of effective electron injection anddurability to oxidation, wherein the aforementioned mixture isexemplified by magnesium/silver mixture, magnesium/aluminum mixture,magnesium/indium mixture, aluminum/aluminum oxide (Al₂O₃) mixture,lithium/aluminum mixture, and aluminum. The cathode can be manufacturedby forming a thin film by vapor deposition or sputtering method of theseelectrode substances. The sheet resistance as the cathode is preferablya few hundred Ω/

or less. The film thickness is preferably 10 nm through 5 μm, morepreferably 50 through 200 nm. To allow passage of the emitted light, ifeither the anode or cathode of the organic EL device is transparent ortranslucent, the light emitting luminance is preferably improved.

After the aforementioned metal is formed on the cathode to a filmthickness of 1 through 20 nm, the transparent conductive film mentionedwith reference to the description of the anode is formed thereon,whereby a transparent or translucent cathode can be produced. This canbe applied to produce a device wherein both the anode and cathode aretransparent.

The following describes the injection layer, blocking layer and electrontransport layer used as the constituent layers of the organic EL deviceof the present invention:

(Injection Layer: Electron Injection Layer and Positive Hole InjectionLayer)

The injection layer is provided as required. It is available in twotypes; an electron injection layer and a positive hole injection layer.It can be located between the anode and light emitting layer or positivehole injection layer, and between the cathode and light emitting layeror electron transport layer, as described above.

The injection layer can be defined as a layer provided between theelectrode and organic layer in order to reduce the drive voltage and toimprove the light emitting luminance. The details are described in the“Organic EL Device and Forefront of its Industrialization”, Part 2,Chapter 2 “Electrode Material”, PP. 123-166, by N.T.S. Nov. 30, 1998. Itis available in two types; a positive hole injection layer (anode bufferlayer) and an electron injection layer (cathode buffer layer).

The details of the anode buffer layer (positive hole injection layer)are disclosed in the Unexamined Japanese Patent Application PublicationsNos. H9-45479, H9-260062 and H8-288069. This layer is exemplified by aphthalocyanine buffer layer as represented by copper phthalocyanine, anoxide buffer layer as represented by vanadium oxide, an amorphous carbonbuffer, and a high molecular buffer layer using a conductive highpolymer such as polyaniline (emeraldine) and polythiophene.

The details of the cathode buffer layer (electron injection layer) aredisclosed in the Unexamined Japanese Patent Application PublicationsNos. H6-325871, H9-17574, and H10-74586. It can be exemplified by ametallic buffer layer represented by strontium and aluminum, an alkalimetal compound buffer layer represented by lithium fluoride, an alkaliearth metal compound buffer layer represented by magnesium fluoride, andan oxide buffer layer represented by aluminum oxide. These buffer layers(injection layers) preferably have a very thin film and the filmthickness is preferably 0.1 nm through 5 μm.

(Blocking Layer: Positive Hole Blocking Layer and Electron BlockingLayer)

As described above, the blocking layer is provided as required, inaddition to the basic constituent layer of the organic compound thinfilm. This is exemplified by the positive hole blocking layer (holeblock layer) disclosed in the Unexamined Japanese Patent ApplicationPublications Nos. H11-204258 and H11-204359, and “Organic EL Device andForefront of its Industrialization”, P. 237 by N.T.S. Nov. 30, 1998.

The positive hole blocking layer in the broader sense is made up of apositive hole blocking material having an electron transport layer and afunction of transporting electrons wherein the capability oftransporting the positive hole is very small. The probability ofreconnection between the electrons and positive hole can be improved bytransporting electrons and blocking the positive hole. Further, thestructure of the electron transport layer can be used, whereverrequired, as the positive hole blocking layer of the present inventionto be described later.

The electron blocking layer in the broader sense is made up of amaterial having a function of the positive hole transport layer and afunction of transporting positive holes wherein the capability oftransporting the electron is very small. The probability of reconnectionbetween the electrons and positive hole can be improved by transportingpositive holes and blocking the electrons. Further, the structure of thepositive hole transport layer can be used, wherever required, as theelectron blocking layer of the present invention to be described later.

(Light Emitting Layer)

The light emitting layer of the present invention can be defined as alayer wherein light is emitted by reconnection of the electron andpositive hole injected from the electron, electron transport layer orpositive hole transport layer. The light emitting portion can be locatedeither inside the light emitting layer or on the interface with theadjacent layer.

The light emitting layer of the organic EL device of the presentinvention preferably contains the following host compound and dopantcompound. This will enhance the light emitting efficiency.

The light emitting can be broadly classified into two types; afluorescent dopant for emitting fluorescent light and a phosphorescentdopant for emitting phosphorescent light.

The former (fluorescent dopant) is exemplified by a coumarin pigment,pyran pigment, cyanine pigment, croconium pigment, squalium pigment,oxobenzanthracene pigment, fluorescein pigment, rhodamine pigment,pyrylium pigment, perylene pigment, stilbene pigment, polythiophenepigment, or rare-earth complex fluorophore.

The latter (phosphorescent dopant) is represented preferably by thecomplex compounds containing the Group VIII, IX and X metals of thePeriodic Table, more preferably by iridium compound and osmium compound.Of these, the indium compound is preferred in particular. The specificexamples are given below:

International Publication No. 00/70655 (leaflet), Unexamined JapanesePatent Application Publications Nos. 2002-280178, 2001-181616,2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060,2001-313178, 2002-302671, 2001-345183 and 2002-324679, InternationalPublication No. 02/15645 (leaflet), Unexamined Japanese PatentApplication Publications Nos. 2002-332291, 2002-50484, 2002-332292,2002-83684, 2002-540572 (Tokuhyo), 2002-117978, 2002-338588,2002-170684, 2002-352960, International Publication No. 01/93642(leaflet), Unexamined Japanese Patent Application Publications Nos.2002-50483, 2002-100476, 2002-173674, 2002-359082, 2002-175884,2002-363552, 2002-184582, 2003-7469, 2002-525808, 2003-7471,2002-525833, 2003-31366, 2002-226495, 2002-234894, 2002-235076,2002-241751, 2001-319779, 2001-319780, 2002-62824, 2002-100474,2002-203679, 2002-100474, 2002-203679, 2002-343572, and 2002-203678.

Some of the specific examples will be given below:

A plurality of types of light emitting dopants may be mixed for use.

<Light Emitting Host>

The light emitting host (also called host) refers to a compound havingthe greatest mixture ratio (mass) in the light emitting layer made up oftwo or more compounds. Other compounds will be called “dopant compounds”(or simply “dopant”). For example, assume that a light emitting layer ismade up of two substances, compounds A and B, and the mixture ratio isA:B=10:90. Then the compound A is the dopant compound, and the compoundB is a host compound. Further, assume that the light emitting layer ismade up of three compounds, compounds A, B and C, and the mixture rationis A:B:C=5:10:85. Then the compounds A and B are dopant compound and thecompound C is a host compound.

There is no structural restriction to the light emitting host used inthe present invention. It is typically represented by a carbazolederivative, triallyl amine derivative, aromatic boron derivative,nitrogen-containing heterocyclic compound, thiophene derivative, furanderivative, a derivative having a basic framework such as anoligoallylene compound, or carboline derivative and diazacarbazolederivative (wherein the diazacarbazole derivative refers to thederivative wherein at least one carbon atom of the hydrocarbon ringconstituting the carboline ring of the carboline derivative is replacedby the nitrogen atom.

Of these, the carboline derivative and diazacarbazole derivative arepreferably utilized.

The following shows specific examples of the carboline derivative anddiazacarbazole derivative without the present invention being restrictedthereto.

The light emitting host used in the present invention can be alow-molecular compound, a high molecular compound having a repeatingunit, or a low-molecular compound having a polymerizable group such asvinyl or epoxy group (vapor deposited polymerizable light emittinghost).

A compound having positive hole and electron transport functions,capable of preventing the increase in the wave length of the emittedlight, and having a high Tg value (glass transition temperature) ispreferably used as a light emitting host. The light emitting host isexemplified by the compounds disclosed in the following documents:Unexamined Japanese Patent Application Publications Nos. 2001-257076,2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786,2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056,2002-334789, 2002-75645, 2002-338579, 2002-105445, 2002-343568,2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453,2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861,2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084, and2002-308837.

A plurality of the commonly known host compounds can be used incombination. A plurality of the dopant compounds can also be used incombination. This permits different beams of light to be mixed, andallows a desired light color to be emitted. Thus, white light can beemitted by adjusting the type of the phosphorescent compound and amountof the dope, and can be used for illumination and backlight.

The color of the light emitted from the organic EL device in the presentinvention is determined by the color when the result of measurement by aspectral radiation luminance meter CS-1000 (by Konica Minolta Sensing)disclosed in “A Handbook of New Color Science” by Japan Society ofColors, the Publishing Organization of the University of Tokyo, 1985. P.108 (FIG. 4.16), is applied to the CIE chromaticity coordinate.

The light emitting layer can be produced by forming the aforementionedcompound into a thin film according to the known thin film formingmethods such as a vapor deposition method, spin coating method, castingmethod, LB method, and inkjet method. There is no particular restrictionto the film thickness of the light emitting layer, but in normal cases,this thickness is preferably 5 nm through 5 μm, more preferably 5through 200 nm. This light emitting layer can be designed to have asingle layer structure made up of one or more than two host compounds.Alternatively, it can be a lamination structure containing a pluralityof layers made up of the same compounds or different types of compounds.

(Positive Hole Transport Layer)

The positive hole transport layer is made of a positive hole transportmaterial having a function of transporting the positive hole, andincludes a positive hole injection layer, electron blocking layer andpositive hole transport layer in the broader sense of the term. A singlepositive hole transport layer or a plurality of positive hole transportlayers can be provided.

The positive hole transport material is either a positive hole injectionfunction or a transport barrier function. It can be either organic orinorganic. For example, it includes triazole derivative, oxydiazolederivative, imidazole derivative, polyallyl alkane derivative,pyrazoline derivative, pyrazolone derivative, phenylene diaminederivative, aryl amine derivative, amino-substituted chalconederivative, oxazole derivative, styryl anthracene derivative, fluorenonederivative, hydrazone derivative, stilbene derivative, silazanederivative, aniline copolymer, conductive high molecular oligomer, andthiophene oligomer in particular.

The aforementioned substances can be used as the positive hole transportmaterials. Use of the porphyrin compound, aromatic tertiary aminecompound, and styryl amine compound, is preferred. Of these compounds,the aromatic tertiary amine compound is preferably used in particular.

The aromatic tertiary amine compound and styryl amine compound istypically exemplified by N,N,N′,N,′-tetraphenyl-4,4′-diamino phenyl;N,N′-diphenyl-N,N′-bis(3-methyl phenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD); 2,2-bis(4-di-p-tolylamino phenyl)propane;1,1-bis(4-di-p-tolylamino phenyl)cyclohexane;N,N,N′,N′-tetra-p-tolyl-4,4′-diamino biphenyl; 1,1-bis(4-di-p-tolylaminophenyl)-4-phenyl cyclohexane;bis(4-dimethylamino-2-methylphenyl)phenylmethane; bis(4-di-p-tolylaminophenyl)phenylmethane;N,N′-diphenyl-N,N′-di(4-methoxyphenyl)-4,4′-diaminobiphenyl;N,N,N′,N′-tetraphenyl-4,4′-diaminodiphenyl ether; 4-4′-bis(diphenylamino)quadriphenyl; N,N,N-tri(p-tolyl)amine;4-(di-p-tolylamino)-4′-[4-(di-p-tolylamino)styryl]stylbene;4-N,N-diphenylamino-(2-diphenylvinyl)benezene;3-methoxy-4′-N,N-diphenylamino stilbenezene; N-phenyl carbazole; and thesubstrates whose the molecule contains two condensed aromatic ringsdisclosed in the Specification of the U.S. Pat. No. 5,061,569 asexemplified by 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD),4,4′,4″-tris[N-(3-methylphenyl)-N-phenyl amino]triphenyl amine (MTDATA)disclosed in the Unexamined Japanese Patent Application Publication No.H4-308688 wherein the triphenyl amine unit is linked with three starburst type.

It is also possible to use the high molecular material wherein thesematerials are introduced into the high molecular chain or thesematerials are used as the principal chain of the high polymer. Further,the inorganic compound of p-type-Si or p-type-SiC can also be used as apositive hole injection material or a positive hole transport material.

The positive hole transport layer can be produced by forming theaforementioned positive hole transport material into a thin film by thecommonly known method such as the vapor deposition method, spin coatingmethod, casting method and printing method including the inkjet method,and LB method. There is no particular restriction to the thickness ofthe film of the positive hole transport layer. Normally this thicknessis preferably about 5 nm through 5 μm, more preferably 5 through 200 nm.The positive hole transport layer can be designed to have a single layerstructure made up of one or more than two of the aforementionedmaterials.

It is also possible to use a positive hole transport layer of highp-type doped with impurities. This is exemplified by the productsdisclosed in the Unexamined Japanese Patent Application PublicationsNos. H4-297076, 2000-196140 and 2001-102175, as well as in J. Appl.Phys., 95, 5773 (2004).

(Electron Transport Layer)

The electron transport layer is made of a material having a function oftransporting the electron, and includes an electron injection layer,positive hole blocking layer and electron transport layer in the broadersense of the term. A single electron transport layer or a plurality ofelectron transport layers can be provided.

In the conventional practice, in the case of a single electron transportlayer or a plurality of electron transport layers, the electrontransport layer (also serving as a positive hole blocking material) usedin the electron transport layer adjacent to the cathode side withrespect to the light emitting layer is only required to have a functionof transmitting the electron injected from the cathode, to the lightemitting layer. A desired material can be selected for use from thecommonly known compounds, which are exemplified by a nitro-substitutedfluorene derivative, diphenyl quinone derivative, thiopyran oxidederivative, carbodiimide, phleonyliden methane derivative, anthraquinodimethane, enthrone derivative and oxadiazole derivative. Further, inthe aforementioned oxadiazole derivative, the quinoxaline derivativecontaining a quinoxaline ring known as an electron suction group and thethiadiazole derivative gained by replacing the oxygen atom of theoxadiazole ring with the sulfur atom can also be used as an electrontransport layer. Further, it is also possible to use the high molecularmaterial wherein these materials are introduced into the high molecularchain or these materials are used as the principal chain of the highpolymer.

A metallic complex of 8-quinolinol derivative exemplified bytris(8-quinolinol)aluminum (Alq),tris(5,7-dichloro-8-quinolinol)aluminum,tris(5,7-dibromo-8-quinolinol)aluminum,tris(2-methyl-8-quinolinol)aluminum,tris(5-methyl-8-quinolinol)aluminum, bis(8-quinolinol)zinc (Znq), or thecomplex wherein the central metal of these metallic complexes isreplaced by In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as an electrontransport material. Further, the substance wherein metal-free, metalphthalocyanine or the terminal thereof is replaced by an alkyl group, orsulfonic acid group can also be preferably used. Further, thedistyrylpyrazine derivative as exemplified as the material of the lightemitting layer can also be used as an electron transport layer.Similarly to the case of the positive hole injection layer and positivehole transport layer, an inorganic semiconductor such as n-type-Si andn-type-SiC can also be used as an electron transport material.

The electron transport layer can be produced by forming theaforementioned electron transport material into a thin film by thecommonly known method such as the vapor deposition method, spin coatingmethod, casting method and printing method including the inkjet method,and LB method. There is no particular restriction to the thickness ofthe film of the electron transport layer. Normally this thickness ispreferably about 5 nm through 5 μm, more preferably 5 through 200 nm.The electron transport layer can be designed to have a single layerstructure made up of one or more than two of the aforementionedmaterials.

It is also possible to use an electron transport layer of high n-typedoped with impurities. This is exemplified by the products disclosed inthe Unexamined Japanese Patent Application Publications Nos. H4-297076,2000-196140 and 2001-102175, as well as in J. Appl. Phys., 95, 5773(2004).

The external take-up efficiency of the light emitted from the organic ELdevice of the present invention at a room temperature is preferably 1%or more, more preferably 5% or more, wherein:

External take-up quantum efficiency (%)=number of the photons emitted tothe organic EL device/the number of electrons flowing to the organic ELdevice×100.

It is also possible to use the hue improving filter such as a colorfilter, or use the color changing filter which uses a fluorophore toconvert into multiple colors the color of light emitted from the organicEL device. When the color changing filter is used, the λmax of the lightemitted from the organic EL device is preferably 480 nm or less.

(How to Manufacture the Organic EL Device)

The following describes the details of how to manufacture the organic ELdevice, with reference to the organic EL device having a structure ofanode/positive hole injection layer/positive hole transport layer/lightemitting layer/electron transport layer/electron injectionlayer/cathode.

A desired electron substance, for example, a thin film made up of ananode substance is formed on the substrate (gas barrier film of thepresent invention) by vapor deposition, sputtering or plasma CVD methodso that the film thickness will be 1 μm or less, preferably 10 through200 nm, whereby an anode is produced. An organic compound thin film madeof the positive hole injection layer, positive hole transport layer,light emitting layer, electron transport layer, electron injection layerand positive hole blocking layer is formed thereon as an organic ELdevice.

This organic compound thin film can be made thin by vapor depositionmethod or wet process (spin coating method, casting method, inkjetmethod and printing method), as described above. The vacuum vapordeposition method, spin coating method, inkjet method or printing methodis used with particular preference because a homogeneous film can beprovided easily and a pin hole does not occur easily. Further, adifferent film forming method can be used for each layer. When a vapordeposition method is used to form a film, the vapor depositionconditions differ according to the type of the compound to be used.Generally, the boat heating temperature is preferably 50 through 450°C., the degree of vacuum is preferably 10⁻⁶ through 10⁻² Pa, vapordeposition speed is preferably 0.01 through 50 nm/sec., the substratetemperature is preferably −50 through 300° C., and the film thickness ispreferably 0.1 nm through 5 μm, more preferably 5 through 200 nm.

After these layers have been formed, a thin film made up of a cathodesubstance is formed thereon to a thickness of 1 μm or less, morepreferably 50 through 200 nm according to the vapor deposition orsputtering method, and a cathode is provided, whereby a desired organicEL device is obtained. This organic EL device is preferably manufacturedin an integrated manner from the positive hole injection layer to thecathode in one evacuation operation. It can be taken out in the middleof the operation and a different film forming method can be applied. Inthis case, consideration must be given in such a way that the work isperformed under the atmosphere of dry inert gas.

It is also possible to reverse the order of production in such a waythat the cathode, electron injection layer, electron transport layer,light emitting layer, positive hole transport layer, positive holeinjection layer and anode are manufactured in that order. When DCvoltage is applied to the multi-color display apparatus obtained in thisway, arrangements are made so that the anode is positive and the cathodeis negative, and voltage of 2 through 40 volts is applied. Then lighthaving been emitted can be observed. Further, AC voltage can also beapplied. It should be noted that there is no restriction to the ACwaveform to be applied.

The display apparatus using the organic EL device in the presentinvention can be used as an indication device, display, or various formsof light emitting source. If three types of organic EL devices—blue, redand green—are used on the indication device and display, a full-colordisplay can be provided.

The indication device and display can be exemplified by a televisionset, personal computer, mobile equipment, AV equipment, text broadcastdisplay, and on-car information display. In particular, they can be usedas a display apparatus for reproducing a still image and motion image.When they are used as a display apparatus for reproducing a movingimage, either a simple matrix (passive matrix) or an active matrix canbe used as a drive method.

The illumination apparatus using the organic EL device of the presentinvention provides a light source for household illumination, on-carillumination, backlight for clocks and liquid crystals, advertisement,traffic signal, optical storage media, electrophotographic photocopiers,optical communications processing equipment and photo sensors, withoutbeing restricted thereto.

The organic EL device of the present invention can also be used as anorganic EL device having a resonator structure. The organic EL devicehaving a resonator structure provides a light source for optical storagemedia, electrophotographic photocopiers, optical communicationsprocessing equipment and photo sensors, without being restrictedthereto. Laser oscillation can be used in the organic EL device of thepresent invention to serve the aforementioned application purposes.

[Display Apparatus]

The organic EL device of the present invention can also be used as onetype of lamps for providing a light source for illumination or exposure.It can also be utilized as a projection apparatus of the imageprojection type, or a display apparatus for direct viewing of a stillimage or motion image. When it is used as a display apparatus for motionimage reproduction, either a simple matrix (passive matrix) or an activematrix can be used as a drive method. A full-color display apparatus canbe provided by employing three or more of the organic EL devices of thepresent invention capable of emitting different colors. Further, using acolor filter, one luminescent color, for example, a white luminescentcolor can be converted into BGR colors, whereby a full color system canbe produced. In this case, the λmax of the light emitted from theorganic EL device is preferably 480 nm or less.

The following describes an example of the display apparatus made of theorganic EL device of the present invention with reference to drawings.

FIG. 8 is a schematic diagram showing a display used in the mobile phoneor the like wherein image information is displayed when light is emittedfrom the organic EL device.

The display 101 includes a display section A having a plurality ofpixels and a control section B for performing image scanning of thedisplay section A based on image information.

The control section B is electrically connected with the display sectionA, and a scanning signal and image data signal are sent to each of thepixels based on the external image information. In response to the imagesignal, pixels for each scanning line are illuminated sequentially bythe scanning signal, and image scanning is performed, whereby imageinformation is displayed on the display section A.

FIG. 9 is a schematic diagram of the display section A.

The display section A includes a wiring section for a plurality ofscanning lines 5 and data lines 106 and a plurality of pixels 103arranged on the substrate. The following describes the major members ofthe display section A. In FIG. 9, the light emitted by the pixel 103 isled in the white-arrowed direction (downward).

The scanning lines 105 and data lines 106 of the wiring section are eachmade up of conductive materials, and the scanning line 105 and datalines 106 intersect at right angles, and are connected to the pixel 103at the position of intersection (details not illustrated).

When a signal is applied from the scanning line 105, the pixel 103receives the image data signal from the data line 106, and light isemitted in response to the image data having been received. The color ofthe emitted light ensures that the pixels in the red, green and blueareas are arranged on one and the same substrate as required, whereby afull color display is provided.

The following describes the pixel light emitting process:

FIG. 10 is a schematic diagram representing a pixel.

The pixel is provided with the organic EL device 110, switchingtransistor 111, drive transistor 112 and capacitor 113. For a pluralityof pixels, the organic EL devices for emitting beams of red, green andblue are used as the organic EL devices 110 are arranged on one and thesame substrate as required, whereby a full color display is provided.

In FIG. 10, an image data signal is applied to the drain of theswitching transistor 111 through the data line 106 from the controlsection B. When the scanning signal is applied to the gate of theswitching transistor 111 through the scanning line 105 from the controlsection B, the drive of the switching transistor 111 is turned on andthe image data signal applied to the drain is transmitted to the gatesof the capacitor 113 and drive transistor 112.

The capacitor 113 is charged in response to the potential of the imagedata signal by the transmission of the image data signal, and the driveof the drive transistor 112 is turned on. The drain of the drivetransistor 112 is connected to the power source line 107, and the sourceis linked to the electrode of the organic EL device 110. Current issupplied to the organic EL device 110 in response to the potential ofthe image data signal applied to the gate.

When the scanning signal has been sent to the scanning line 105 by thesequential scanning of the control section B, the drive of the switchingtransistor 111 is turned off. However, even if the drive of theswitching transistor 111 is turned off, the capacitor 113 maintains thepotential of the charged image data signal. Accordingly, the drive ofthe drive transistor 112 is kept turned on, and hence, the lightemission of the organic EL device 110 is maintained until the nextscanning signal is applied. When the next scanning signal has beenapplied by sequential scanning, the drive transistor 112 is driven inresponse to the potential of the next image data signal synchronizedwith the scanning signal, whereby the organic EL device 110 emits light.

To be more specific, for the organic EL device 110, the switchingtransistor 111 as an active device and the drive transistor 112 areprovided on the organic EL devices 110 of each of the pixels, wherebylight is emitted from the organic EL device 110 of each of a pluralityof pixels 103. This is called an active matrix light emission method.

In this case, the light emitted from the organic EL device 110 can beeither the light emitted in a plurality of gradations by the multilevelimage data signal having a plurality of gradation potentials, or thelight wherein emission of a predetermined amount of light is turned onor off by binary image data signal.

The potential of the capacitor 113 can be maintained until the nextscanning signal is applied, or can be discharged immediately before thenext scanning signal is applied.

In the present invention, the light emission drive system can be eitherthe aforementioned active matrix system, or the passive matrix systemwherein organic EL device emits light in response to the data signalonly when the scanning signal has been scanned.

FIG. 11 is a schematic diagram representing the display apparatus basedon the passive matrix system. In FIG. 11, the scanning line 105 and dataline 106 are arranged face to face with each other, with the pixel 103sandwiched in-between.

When the scanning signal of the scanning line 105 is applied by thesequential scanning, the pixel 103 connected to the scanning line 105 tobe applied emits light in response to the image data signal. In thepassive matrix system, the pixel 103 has no active device, and reductionin the production cost can be achieved.

[Illumination Apparatus]

The organic EL device of the present invention as the illuminationapparatus can be applied to the organic EL device wherein the virtuallywhite light is emitted. A plurality of colors are emitted simultaneouslyby a plurality of light emitting materials, and a white light is emittedthrough color mixture. The combination of a plurality of emitted lightcolors may include three maximum emission wavelengths of three primarycolors of blue, green and blue, or two maximum emission wavelengthsusing the relationship of complementary colors such as blue and yellow,and bluish green and orange colors.

The combination of the light emitting materials for getting a pluralityof light colors can be either a combination of a plurality of thematerials emitting a plurality of phosphorescent or fluorescent beams(light emitting dopant), or a combination of the light emitting materialfor emitting phosphorescent or fluorescent light, and the pigmentmaterial for emitting light using the light from the light emittingmaterial as the excitation light. In the white organic EL device of thepresent invention, a combination of a plurality of light emittingdopants is preferably used.

The layer structure of the organic EL device for getting a plurality oflight colors can be formed by the method of allowing a plurality oflight emitting dopants to be present in one light emitting layer; themethod wherein a plurality of light emitting layers are provided and thedopants having different light emitting wavelengths are present in eachlight emitting layer; and the method wherein the fine pixel for emittinglight to the different waveforms is created on the shape of a matrix.

In the white organic EL device of the present invention, patterning canbe performed according to the metal mask and inkjet printing method atthe time of film formation as required. When patterning is to beperformed, patterning can be applied to the electrode alone, to both theelectrode and light emitting layer, or to the entire layer of thedevice.

There is no particular restriction to the light emitting material usedin the light emitting layer. For example, in the case of a backlight inthe liquid crystal device, the color can be converted into white bycombination of the white complex of the present invention or any otherdesired one selected from the commonly known light emitting materials,so as to conform to the range of wavelength corresponding to the CF(color filter) characteristics.

As described above, in addition to the indication device and display,the white organic EL device can be used preferably as various types oflight emitting light sources for household illumination, on-carillumination. It can also be employed as one of the lamps such asexposure light sources for the backlight of the liquid crystal display,and display apparatus.

Further, the white organic EL device can be used preferably as a lightsource for backlight for clocks, advertisement, traffic signal, opticalstorage media, electrophotographic photocopiers, optical communicationsprocessing equipment and optical sensors. It can also be used over anextensive range including the general household electric appliancesrequiring a display apparatus.

EXAMPLES

The following describes the present invention with reference to theexample, without the present invention being restricted thereto.

Example 1

Plasma discharge processing was performed using the roll electrode typedischarge processing apparatus shown in FIG. 4, and a ceramic film wasformed on the substrate film. In the discharge processing apparatus, aplurality of rod-like electrodes were placed face to face with the rollelectrode, parallel to the conveying direction of the film in such a waythat the materials (discharge gas, reaction gas 1, 2 (to be describedlater)) can be supplied to each electrode.

The dielectric for coating each electrode, together with the opposingelectrode, was coated on the ceramic sprayed electrode to a thickness of1 mm on one side. After coating, the gap between the electrodes was setto 1 mm. Further, the base metal coating the dielectric was designed asa stainless steel jacket having a cooling function by coolant. Electrodetemperature was controlled by coolant during the process of discharging.The light source used in this case was a high frequency power sourcemanufactured by Applied Electrical Equipment (80 kHz), and a highfrequency power source manufactured by Pearl Industries (13.56 MHz).Other conditions are as described below:

The substrate films were formed on the PEN film (150 μm thick) withacryl clear hard coated layer in the order of a closely bonded layer, aceramic layer and a protective layer, as described below. The filmthickness was 10 nm for the closely bonded layer, 50 nm for the ceramiclayer and 50 nm for the protective layer. The temperature of thesubstrate film at the time of film formation was kept at 120° C.

Samples Nos. 1 through 5 as gas barrier films were produced under thefollowing layer forming conditions while changing the power of the highfrequency power source for formation of the ceramic layer.

In the following process, a closely bonded layer and a protective layer(film) were laminated in addition to the ceramic layer (film) of thepresent invention, wherein the generating conditions were changed.

<Ceramic Layer>

Discharge gas: N₂ gas

Reaction gas 1: 5% by volume of oxygen gas with respect to all the gases

Reaction gas 2: 0.1% by volume of tetraethoxy silane (TEOS) with respectto all the gases

Power of low frequency power source: 80 kHz at 10 W/cm²

Power of high frequency power source: 13.56 kHz at 1 through 10 W/cm²

The composition of this ceramic layer was SiO₂ for Samples Nos. 1through 5. The density was 2.07 for Sample No. 1, 2.11 for Sample No. 2,2.13 for Sample No. 3, 2.18 for Sample No. 4, and 2.20 for Sample No. 5.

<Closely Bonded Layer>

Discharge gas: N₂:

Reaction gas 1: 1% by volume of hydrogen gas with respect to all thegases

Reaction gas 2: 0.5% by volume of tetraethoxy silane (TEOS) with respectto all the gases

Power of low frequency power source: 80 kHz at 10 W/cm²

Power of high frequency power source: 13.56 kHz at 10 W/cm²

The composition of this closely bonded layer was SiO_(1.48) C_(0.96),and the density was 2.02.

<Protect Layer>

Discharge gas: N₂:

Reaction gas 1: 1% by volume of hydrogen gas with respect to all thegases

Reaction gas 2: 0.5% by volume of tetraethoxy silane (TEOS) with respectto all the gases

Power of low frequency power source: 80 kHz at 10 W/cm²

Power of high frequency power source: 13.56 kHz at 5 W/cm²

The composition of this protective layer was SiO_(1.48) C_(0.96), andthe density was 2.03.

<How to Measure the Gas Barrier Performance>

The WOPET-003 of Creatic Inc. was used to measure the vapor barrierperformance (permeability) of the ceramic film and oxygen barrierperformance (permeability) of the ceramic film.

Up to the order of 10⁻², the reference samples were compared andevaluated by the Model OX-TRAN2/21-L oxygen permeability measuringinstrument and Model PERMATRAN-w3/33G vapor permeability measuringinstrument of Mocon Inc. After that, calibration was made with referenceto the instrument of Mocon Inc., and extrapolation was made bysimulation up to the order of 10⁻⁷.

<Measuring the Density Ratio>

Baking was performed at 1100° C. using a silicon substrate as the filmdensity (ρb) of the bulk ceramic (silicon oxide: SiO₂), and a thermallyoxidized film was formed on the surface to a thickness of 100 nm. Thedensity of the thermally oxidized film was obtained by X-rayreflectivity measurement, and was found to be 2.20. This value was usedas representing the density (ρb) of the bulk silicon oxide film.

Further, while changing the electric power of the high frequency sidepower source, the density (ρf) of the ceramic film (silicon oxide film)having been formed was calculated by the same X-ray reflectivitymeasurement for each sample with a ceramic film formed thereon.

In the measurement of the X-ray reflectivity, the Model MXP21 ofMacScience Inc. was used as a measuring instrument, and copper was usedas a X-ray source target. The instrument was operated at a voltage of 42kV with a current of 500 mA. A multi-layer film parabola mirror was usedon the incident monochrometer. The incident slit was 0.05 mm×5 mm, andthe light receiving slit was 0.03 mm×20 mm. According to the 2θ/θscanning process, measurement was conducted by the FT method in therange of 0 through 5° at a step width of 0.005°, 10 seconds per step.Curve fitting was applied to the reflectivity curve having beenobtained, using the Reflectivity Analysis Program Ver. 1 of MacScienceInc., and parameters were obtained in such a way that the residual sumof squares between the actually measured value and fitting curve wouldbe minimized. Then the density of each parameter was obtained from eachparameter.

The density ratio was obtained for each of the samples from the density(ρf) of the ceramic (silicon oxide) layer formed by the plasma CVDmethod under atmospheric pressure and the density (ρb) of the ceramic(silicon oxide) layer.

TABLE 1 High Vapor frequency Density barrier Sample power ratioperformance No. (W/cm²) (=ρf/ρb) (g/m²/day) Remarks 1 1 0.94 1.3Comparative example 1 2 3 0.96 8 × 10⁻⁴ Present invention 3 5 0.97 3 ×10⁻⁴ Present invention 4 7 0.99 6 × 10⁻⁵ Present invention 5 10 1 2 ×10⁻⁶ Present invention

TABLE 2 High Oxygen frequency Density barrier Sample power ratioperformance No. (W/cm²) (=ρf/ρb) (g/m²/day) Remarks 1 1 0.94 2.5Comparative example 1 2 3 0.96 8 × 10⁻² Present invention 3 5 0.97 3 ×10⁻² Present invention 4 7 0.99 6 × 10⁻³ Present invention 5 10 1 2 ×10⁻⁴ Present invention

In Tables 1 and 2, the unit of the vapor permeability is g/m²/day, andthat of oxygen permeability is ml/m²/day. The description in Tables 1and 2 reveal that, if the density ratio is kept within the range of thepresent invention, both the vapor and oxygen barrier performances arehigh.

Example 2

A film having the following thickness was formed on the substrateaccording to the same procedure as that used in the Example 1, using theModel PD-270STP plasma CVD apparatus of Sanco Inc.

The following describes the film forming conditions for each layer inSamples Nos. 6 through 10:

<Ceramic Layer>

Oxygen pressure: Gas pressure was changed at 13.3 through 133 Pa

Reaction gas: Tetraethoxy silane (TEOS), 5 sccm (standard cubiccentimeter per minute)

Power: 100 W at 13.56 MHz

Retained substrate temperature: 120° C.

<Closely Bonded Layer and Protective Layer>

The power application was reversed under the aforementioned ceramiclayer film making conditions, and the substrate holding side was used asthe ground. Then high frequency power was applied to the side of theopposed electrode, whereby a film was formed. The composition of theprotective layer and closely bonded layer of each sample wasSiO_(1.48)C_(0.96). The density of the protective layer and closelybonded layer was 2.08 for the sample No. 6, 2.05 for the sample No. 7,2.02 for the sample No. 8, 1.98 for the sample No. 9 and 1.96 for thesample No. 10.

Similarly to the above case, a test was made to evaluate the densityratio (=ρf/ρb) of the ceramic layer of the gas barrier film having beenformed with respect to the bulk film, and the residual stress. The gasbarrier performance was also evaluated, similarly to the case of Example1.

<Residual Stress Evaluation Procedure>

A barrier film was formed on a quartz glass having a thickness of 100μm, a width of 10 mm and a length of 50 mm to a thickness of 1 μm. Theresidual stress was measured by the Model MH4000 thin film physicalproperty evaluation apparatus of NEC-Sanei Inc. (MPa).

The gas barrier performance was measured twice to get the values in theinitial stage and after the lapse of repeated thermo conditions. To bemore specific, the sample was left to stand at 23° C. with a relativehumidity of 55% RH for 24 hours and the temperature was changed from −40to 85° C. 300 times in 30 minutes. After that, vapor and oxygen barrierperformances were measured.

The following shows the result of the test. It should be noted that “−”in the column of gas pressure in Tables 3 and 4 indicates atmosphericpressure.

TABLE 3 Vapor barrier performance (g/m²/day) Gas Density After Sam-pres- ratio repeated ple sure (=ρf/ thermo No. (Pa) ρb) Stress Initialconditions Remarks 6 26.6 0.97 100 MPa 7 × 10⁻³ 2 × 10⁻² Presentinvention 7 39.9 0.97 80 MPa 4 × 10⁻³ 4 × 10⁻³ Present invention 8 53.20.97 50 MPa 3 × 10⁻³ 3 × 10⁻³ Present invention 5 — 1 0.9 MPa 2 × 10⁻⁶ 3× 10⁻⁶ Present invention 9 60.0 0.97 15 MPa 1 × 10⁻³ 5 × 10⁻³ Presentinvention 10 63.8 0.97 5 MPa 5 × 10⁻⁴ 4 × 10⁻⁴ Present invention

TABLE 4 Oxygen barrier performance (ml/m²/day) Gas Density After Sam-pres- ratio repeated ple sure (=ρf/ thermo No. (Pa) ρb) Stress Initialconditions Remarks 6 26.6 0.97 100 MPa 4 × 10⁻² 9 × 10⁻² Presentinvention 7 39.9 0.97 80 MPa 3 × 10⁻² 3 × 10⁻² Present invention 8 53.20.97 50 MPa 6 × 10⁻³ 6 × 10⁻³ Present invention 5 — 1 0.9 MPa 2 × 10⁻⁴ 2× 10⁻⁴ Present invention 9 60.0 0.97 15 MPa 3 × 10⁻³ 5 × 10⁻³ Presentinvention 10 63.8 0.97 5 MPa 3 × 10⁻⁴ 4 × 10⁻⁴ Present invention

Example 3 Formation of Transparent Conductive Film

A transparent conductive film was formed on the ceramic film of thesample No. 5 of the gas barrier film produced in the Example 1 by thefollowing method.

A plasma discharging apparatus having parallel flat electrodes wasutilized, and the aforementioned transparent film was mounted betweenthese electrodes. Then a gas mixture was introduced to form a thin film.

In the ground electrode, the stainless steel plate measuring 200 mm×200mm×2 mm was coated with a closely bonded alumina sprayed film. Afterthat, the solution formed by diluting the tetramethoxy silane with ethylacetate was coated and dried. Then it was cured by ultraviolet rays, andwas provided with pore sealing treatment. Then the dielectric surfacecoated in this manner was polished and smoothed, and the electrode wasprocess so that the Rmax value would be 5 μm. The applied electrode usedwas arranged in such a way that the hollow rectangular pure titaniumpipe was coated with the dielectric under the same conditions as thoseof the ground electrode. A plurality of applied electrodes weremanufactured and were arranged face to face with the ground electrode,thereby creating a discharging space.

The Model JRF-10000 high frequency power source of Nippon Denshi Inc.was used as the power source used for plasma generation. The power of 5W/cm² at a frequency of 13.56 MHz was supplied.

The gas mixture of the following composition was fed between electrodesto create a state of plasma. The aforementioned gas barrier film wassubjected to plasma processing under atmospheric pressure, and the tindoped indium oxide (ITO) was formed on the gas barrier layer (ceramicfilm) to a thickness of 100 nm.

Discharge gas: 98.5% by volume of helium

Reaction gas 1: 0.25% by volume of oxygen

Reaction gas 2: 1.2% by volume of indium acetyl acetonate

Reaction gas 3: 0.05% by volume of dibutyl tin diacetate

(Production of Organic EL Device)

The gas barrier film (100 mm×100 mm) with the aforementioned ITO filmformed thereon was used as a substrate. After having been subjected topatterning, the gas barrier film provided with the ITO transparentelectrode was ultrasonically cleaned by isopropyl alcohol, and was driedby dry nitrogen gas. This transparent support substrate was fixed on thesubstrate holder of a vacuum vapor deposition apparatus available on themarket. In the meantime, 200 mg of m-NPD was put into a molybdenum-maderesistance heating boat, and 200 mg of CBP as a host compound was put inanother molybdenum-made resistance heating boat. Further, 200 mg ofbathocuproin (BCP) was put in still another molybdenum-made resistanceheating boat, 100 mg of Ir-1 was put in a further molybdenum-maderesistance heating boat, and 200 mg of Alq₃ was put in a still furthermolybdenum-made resistance heating boat. This was mounted on the vacuumvapor deposition apparatus.

Then the pressure of the vacuum tank was reduced down to 4×10⁻⁴ Pa andan electrical current was applied to the aforementioned heating boatfilled with α-NPD so that the mixture was heated. The mixture wasvapor-deposited on the transparent support substrate at a vapordeposition speed of 0.1 nm per second and a positive hole transportlayer was formed. Further, an electrical current was applied to theaforementioned heating boats filled with CBP and Ir-1 so that themixture was heated. The mixtures were vapor-deposited on theaforementioned positive hole transport layer, and were each at a vapordeposition speeds of 0.2 nm and 0.012 nm per second and a positive holetransport layer was formed. Thus, a light emitting layer was formed. Thesubstrate temperature was equal to the room temperature at the time ofvapor deposition. Further, an electrical current was applied to theaforementioned heating boat filled with BCP so that the mixture washeated. The mixture was vapor-deposited on the light emitting layer at avapor deposition speed of 0.1 nm per second and a positive hole blockinglayer was formed to a thickness of 10 nm. Further, an electrical currentwas applied to the aforementioned heating boat filled with Alq₃ so thatthe mixture was heated. The mixture was vapor-deposited on theaforementioned positive hole blocking layer at a vapor deposition speedof 0.1 nm per second and a positive hole transport layer was formed to athickness of 10 nm. The substrate temperature was equal to the roomtemperature at the time of vapor deposition.

This was followed by the step of vapor deposition of 0.5 nm of lithiumfluoride and 110 nm of aluminum, whereby a cathode was formed and anorganic EL device was produced.

(Production of Sealing Film 1)

Polypropylene was laminated to a thickness of 30 μm on one side of thealuminum foil having a thickness of 30 μm. The other side of this foilwas subjected to discharge processing, using a roll electrode typedischarge processing apparatus used in Example 1 and shown in FIG. 4.Then the same a ceramic (SiO₂) film as that of the Example 1 was formedto a thickness of 30 nm under the following conditions, whereby asealing film was produced.

<Ceramic Layer>

Discharge gas: N₂ gas

Reaction gas 1: 5% by volume of oxygen gas with respect to all the gases

Reaction gas 2: 0.1% by volume of tetraethoxy silane (TEOS) with respectto all the gases

Power of low frequency power source: 80 kHz at 10 W/cm²

Power of high frequency power source: 13.56 kHz at 10 W/cm²

Under the environment wherein air was purged by nitrogen gas (inertgas), the SiO₂ side of the sealing film 1 and the cathode side of theorganic EL device were bonded using an epoxy based adhesive, also, theSiO₂ side of the sealing film 1 and the surrounding area of the gasbarrier film where the organic EL device was not provided thereon werebonded using the epoxy based adhesive, whereby the device was sealed,and an organic EL device 1 was produced.

(Production of Sealing Film 2)

Polypropylene was laminated to a thickness of 30 μm on one side of thealuminum foil having a thickness of 30 μm, whereby a sealing film 2 wasproduced.

Under the environment wherein air was purged by nitrogen gas (inertgas), the side of the sealing film 2 not provided with polypropylenefilm (metallic surface of the aluminum foil) was bonded to the cathodesurface of the organic EL device, and to the surrounding area withoutthe organic EL device of gas barrier film being formed thereon, using anepoxy based adhesive, whereby an organic EL device 2 was produced.

(Evaluation of Organic EL Device)

An electrical current was applied to the organic EL device having beenproduced, under the conditions of high temperature and high humidityregistering 60° C. with a relative humidity of 95% RH, and the presenceor absence of a dark spot was checked.

The examination has revealed that both organic EL devices 1 and 2 weresatisfactory, and the organic EL devices produced by the sealing methodof the present invention exhibited excellent sealing performances withdark spots hardly occurring. In particular, the rate of occurrence ofdark spots was smaller in the organic EL device 1 wherein a ceramic filmwas formed on the aluminum foil, and this surface was bonded with thecathode by sealing.

1. A gas barrier film comprising a resin substrate provided thereon atleast one layer of a ceramic film, wherein the density ratio Y (=ρf/ρb)satisfies 1≧Y≧0.95 and the ceramic film has a residual stress being acompression stress of 0.01 MPa or more and 100 Mpa or less, wherein ρfis the density of the ceramic film and ρb is the density of acomparative ceramic film being formed by thermal oxidation or thermalnitridation of a metal as a mother material of the ceramic film so as tobeing the same composition ratio of the ceramic film.
 2. The gas barrierfilm described of claim 1, wherein the density ratio Y (=ρf/ρb)satisfies 1≧Y≧0.98.
 3. The gas barrier film of claim 1, wherein theresidual stress is 0.01 MPa or more and 10 Mpa or less.
 4. The gasbarrier film of claim 1, wherein a material constituting the ceramicfilm is a silicon oxide, a silicon oxide-nitride, a silicon nitride, ofan aluminum oxide, or a mixture thereof.
 5. A resin substrate for anorganic electroluminescent element comprising the gas barrier film ofclaim 1 provided thereon a transparent conductive thin film.
 6. Anorganic electroluminescent element being formed by providing a resinsubstrate of claim 5, coating a phosphorescence emitting organicelectroluminescent material layer and a metal layer as a cathode on theresin substrate and, sealing with adhesion of a metal foil laminated ona resin layer.
 7. The organic electroluminescent element of claim 6,wherein the metal foil laminated on the resin layer comprises the metalfoil, the resin layer at the other side of a metal cathode against themetal foil and a ceramic layer at the side of the metal cathode againstthe metal foil, wherein the density ratio Y (=ρf/ρb) satisfies 1≧Y≧0.95and the ceramic film has a residual stress being a compression stress of0.01 MPa or more and 100 Mpa or less, wherein ρf is the density of theceramic film and ρb is the density of a comparative ceramic film beingformed by thermal oxidation or thermal nitridation of a metal as amother material of the ceramic film so as to being the same compositionratio of the ceramic film.
 8. A method of manufacturing a gas barrierfilm comprising: exciting a gas containing a thin film forming gas witha high frequency electric field under atmospheric pressure or a pressureclose to the atmospheric pressure and exposing a resin substrate to theexcited gas so as to form at least one layer of a ceramic film on theresin substrate, wherein the density ratio Y (=ρf/ρb) satisfies 1≧Y≧0.95and the ceramic film has a residual stress being a compression stress of0.01 MPa or more and 100 Mpa or less, wherein ρf is the density of theceramic film and ρb is the density of a comparative ceramic film beingformed by thermal oxidation or thermal nitridation of a metal as amother material of the ceramic film so as to being the same compositionratio of the ceramic film.
 9. The method of manufacturing a gas barrierfilm of claim 8, wherein the gas contains a nitrogen gas in an amount of50% by volume or more.
 10. The method of manufacturing a gas barrierfilm of claim 8, wherein the high frequency electric field is one inwhich a first high frequency electric field and a second high frequencyelectric field are superimposed, the frequency ω₂ of the second highfrequency electric field is higher than the frequency ω₁ of the firsthigh frequency electric field, and the relationship among the intensityV₁ of the first high frequency field, the intensity V₂ of the secondhigh frequency field and the intensity IV of a discharge startingelectric field satisfy the formula of V₁≧IV>V₂ or the formula ofV₁>IV≧V₂.
 11. The method of manufacturing a gas barrier film of claim10, wherein output density of the second high frequency electric fieldis 1 W/cm² or more.